WO2021246458A1 - Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

Provided are: a photosensitive resin composition containing at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole, and also containing a compound B that has a photodimerizable group and an alkoxysilyl group; a cured film obtained by curing the photosensitive resin composition; a laminate including the cured film; a method for producing the cured film; and a semiconductor device including the cured film or the laminate.

Description

Photosensitive resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device

The present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.

Polyimide or polybenzoxazole is applied to various applications because it has excellent heat resistance and insulating properties. The application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, the polyimide or polybenzoxazole is a form of a photosensitive resin composition containing at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor. Used in.
Such a photosensitive resin composition is applied to a base material by, for example, coating to form a resin film, and then exposed, developed, heated or the like as necessary to form a cured film on the base material. Can be formed.
The polyimide precursor and the polybenzoxazole precursor are cyclized by heating, for example, and become polyimide and polybenzoxazole in the cured membrane, respectively.
Since the photosensitive resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied photosensitive resin composition at the time of application. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide, polybenzoxazole, etc., from the viewpoint of excellent manufacturing adaptability, the industrial application of the above-mentioned photosensitive resin composition is expected more and more.

For example, Patent Document 1 describes (A) an acrylic copolymer having a photodimerization moiety composed of a hydrophobic group and a thermally crosslinked moiety composed of a hydrophilic group, and (B) a polyimide precursor having an aromatic ring moiety. (C) A resin composition containing a cross-linking agent for cross-linking the component (A) and the component (B) is described.
Patent Document 2 describes a liquid crystal aligning agent for photoalignment containing a polymer component having a structural unit containing a photoreactive structure, wherein the polymer component is a monomer containing at least a first monomer and a second monomer. The first monomer is composed of a polymer obtained by polymerizing a composition or a derivative thereof, and the first monomer contains a photoreactive structure in a portion forming a structural unit of the polymer and forms a structural unit of the polymer. The portion to be heated contains a structure that causes a chemical reaction by heating, and the second monomer contains a photoreactive structure in a portion forming a constituent unit of the polymer, and a portion forming the constituent unit of the polymer. Describes a liquid crystal aligning agent for photoalignment, which has a structure that does not cause a chemical reaction due to heating.

International Publication No. 2012/018121 Japanese Unexamined Patent Publication No. 2019-21177

A photosensitive resin composition capable of forming a finer pattern by exposure and development is desired.
In the present specification, the ability to form a fine pattern is also referred to as being excellent in pattern formability.

The present invention relates to a photosensitive resin composition having excellent pattern-forming properties, a cured film obtained by curing the photosensitive resin composition, a laminate containing the cured film, a method for producing the cured film, and the cured film. Alternatively, it is an object of the present invention to provide a semiconductor device including the above-mentioned laminate.

Examples of typical embodiments of the present invention are shown below.
<1> At least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide and a polybenzoxazole, and
A photosensitive resin composition containing a group capable of a photodimerization reaction and compound B, which is a compound having an alkoxysilyl group.
<2> The photosensitive resin composition according to <1>, wherein the photodimerizable group in the compound B has a cinnamoyl structure, a coumarin structure, a naphthalene structure, or an anthracene structure.
<3> The photosensitive resin composition according to <1> or <2>, wherein the compound B is a compound represented by the following formula (1-1) or the following formula (1-2).

In formula (1-1), R ¹ independently represents a monovalent organic group, n represents an integer of 0 to 5, and T ¹ and T ² independently represent a hydrogen atom or a monovalent organic. A group is represented, X ¹ is a divalent linking group, and Z ¹ is an alkoxysilyl group.
In formula (1-2), R ¹ independently represents a monovalent organic group, m represents an integer of 0 to 4, and T ³ to T ⁶ independently represent a hydrogen atom or a monovalent organic. Representing a group, X ² and X ³ each independently represent a divalent linking group, and Z ² and Z ³ each independently represent an alkoxysilyl group.
<4> Any one of <1> to <3> further containing compound C, which is a compound having no at least one of a photodimerizable group and an alkoxysilyl group and having an azole group. The photosensitive resin composition according to.
<5> The photosensitive according to any one of <1> to <4>, wherein the compound C is a compound having no alkoxysilyl group, a group capable of photodimerization reaction, and an azole group. Resin composition.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the compound C is a resin.
<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the compound B is a resin.
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the compound B contains an azole group.
<9> The photosensitive resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9>.
<11> A laminate containing two or more layers of the cured film according to <10> and containing a metal layer between any of the cured films.
<12> A method for producing a cured film, which comprises a film forming step of applying the photosensitive resin composition according to any one of <1> to <9> to a substrate to form a film.
<13> The method for producing a cured film according to <12>, which comprises an exposure step for exposing the film and a developing step for developing the film.
<14> The method for producing a cured film according to <12> or <13>, which comprises a heating step of heating the film at 50 to 450 ° C.
<15> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.

According to the present invention, a photosensitive resin composition having excellent pattern forming properties, a cured film obtained by curing the photosensitive resin composition, a laminate containing the cured film, a method for producing the cured film, and the above. A semiconductor device including a cured film or the above-mentioned laminate is provided.

Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, a combination of preferred embodiments is a more preferred embodiment.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, polyimide and polybenzoxazole (hereinafter, also referred to as "specific resin"), and , A group capable of photodimerization reaction, and compound B, which is a compound having an alkoxysilyl group.

The photosensitive resin composition of the present invention may be a negative type photosensitive resin composition or a positive type photosensitive resin composition, but a negative type photosensitive resin composition is preferable. ..
The negative type photosensitive resin composition refers to a composition in which an unexposed portion (non-exposed portion) is removed by a developing solution when a layer formed from the photosensitive resin composition is exposed.
The positive type photosensitive resin composition refers to a composition in which an exposed portion (exposed portion) is removed by a developing solution when a layer formed from the photosensitive resin composition is exposed.

The photosensitive resin composition of the present invention is excellent in pattern forming property.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.

The photosensitive resin composition of the present invention contains compound B, which is a compound having a group capable of photodimerization reaction and an alkoxysilyl group. When such a composition is exposed, it is presumed that a part of the exposure light can be absorbed by the above compound and the exposure amount is unlikely to be excessive, so that the pattern shape after development is improved and the pattern formability is excellent. To.
In particular, when the compound B has an azole group and the composition is applied on a metal support for patterning, the compound B is used because the azole group is coordinated to the metal. It is considered to be unevenly distributed near the metal support (deep part of the film). Therefore, it is considered that the influence of the reflection of the exposure light by the metal layer can be suppressed, the pattern shape after development is further improved, and the pattern formability is excellent.
Further, in a system in which radical polymerization or cationic polymerization occurs during exposure, polymerization in the deep part of the membrane, which is less affected by polymerization inhibition by oxygen or water, may be excessive. However, as described above, the compound B having a group capable of photodimerization reaction is unevenly distributed in the deep part of the film, so that a part of the exposure light is absorbed, so that the above-mentioned excessive polymerization is suppressed, and particularly in the deep part of the film. It is considered that the pattern shape in the above is easily improved and the pattern formability is excellent.

Further, in the cured film, the compound B becomes a resin-like compound by a bond formed by photodimerization of the photodimerizable group and a bond formed by condensation of an alkoxysilyl group. It is presumed that the interaction between this resin-like compound and the support (for example, a metal support) also improves the adhesion.
In particular, when the compound B has an azole group and the composition is applied onto a metal support for patterning, the azole group in the resin-like compound is coordinated to the metal. It is considered that the adhesion between the obtained cured film and the metal support is also improved.

Here, Patent Documents 1 and 2 do not describe or suggest a photosensitive resin composition containing a group capable of photodimerization reaction and a compound having an alkoxysilyl group.

Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

<Specific resin>
The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.
The photosensitive resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.

Moreover, it is preferable that the specific resin has a polymerizable group.
Examples of the polymerizable group in the specific resin include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group and an alkoxymethyl group.
As the radically polymerizable group, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group, and a (meth) acryloyloxy group is preferable.

Among these, the specific resin preferably contains a radically polymerizable group.
When the specific resin has a radically polymerizable group, the photosensitive resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described later as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described below, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a photosensitive resin composition, for example, a negative photosensitive layer is formed.
Further, the specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator described later as a photosensitive agent. From such a photosensitive resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.

[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2).
Equation (2)

In formula (2), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ^113. And R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group.

^{A 1} and A ² in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
^{R 111} in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified. A cyclic aliphatic group having 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by —L—Ar— is exemplified. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —C (= O) −, —S—, —SO. ₂ -, NHCO-, or is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - C ( = O) -, - S-, or, -SO ₂ -, more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, - C (CF 3 ) _2- or -C (CH ₃ ) _2- is more preferable.
In the formula, * represents a binding site with another structure.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-,1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenyl sulfone, 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino) -4-Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) ) Sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'- Dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-) Aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4, 4'-Diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4 , 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane , Diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octa Fluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-Bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4, 4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluo) Lomethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2, 2-Bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'- At least one selected from diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl. Diamine can be mentioned.

Further, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.

In addition, the following diamines can also be preferably used.

Further, a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.

R ¹¹¹ is preferably represented by −Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO ₂ - are preferred. The aliphatic hydrocarbon group here is preferably an alkylene group.

Further, ^{from the viewpoint of i-ray transmittance, R 111} is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and ^{at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoro. It is a methyl group.
The ^{monovalent organic group of R 50} to R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

Further, R ¹¹¹ may have a structure containing a polymerizable group.
For example, R ¹¹¹ may have a structure derived from a diamine compound having a polymerizable group.
The diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and is a compound having a structure in which a structure containing an amino group and a polymerizable group is directly linked to the aromatic ring structure. Is more preferable.
As the polymerizable group, an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide are preferable. A group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.

When R ¹¹¹ has a structure containing a polymerizable group, it is preferable that R ¹¹¹ has a structure represented by the following formula (1-1).

In formula (1-1), Y ¹ represents an n + divalent group containing an aromatic hydrocarbon group, P ¹ represents a group containing a polymerizable group, n represents an integer of 1 or more, and * represents each. , Represents the bonding site with the nitrogen atom to which ^{R 111} in the formula (2) is bonded.

-Y ^1-
In formula (1-1), Y ¹ represents an n + divalent group containing an aromatic hydrocarbon group.
Aromatic hydrocarbon group for Y ¹ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, 2 or more benzene rings It is more preferable that the group is obtained by removing the hydrogen atom of, and it is particularly preferable that the group is obtained by removing 3 or more hydrogen atoms from the benzene ring.
In the formula (1-1), in Y ^1, binding site of two * and according to equation (1-1) is preferably either an aromatic hydrocarbon group. That is, the two * is described in equation (1-1), an aromatic hydrocarbon ring structure contained in Y ^1, it is preferable to directly bond.
In the formula (1-1), in ^{Y 1,} binding site of the ^{P 1} is preferably either an aromatic hydrocarbon group. That is, it is preferable that P ¹ is directly bonded to the aromatic hydrocarbon ring structure contained ^{in Y 1.}

Y ¹ preferably contains at least one structure selected from the group consisting of the structures represented by the following formulas (A2-1) to (A2-5), and the above-mentioned formulas (A2-1) to Y1. It is more preferable that the structure is at least one selected from the group consisting of the structures represented by the formula (A2-5).

Wherein ^{(A2-1) ~ (A2-5),} R A211 ~ R A214, R A221 ~ R A224, R A231 ~ R A238, R A241 ~ R A248 and ^R A251 ^{~ R A258} are each independently a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and ^LA231 and ^LA241 are independently single-bonded, carbonyl group, sulfonyl group, and divalent, respectively. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene ^group, at least one of R A211 ^{~ R A214,} at least one of R a 221 ^{~ R A224 one,} at least one of ^R A231 ^~ R ^A238, at least one of R a 241 ^{~ R A248, and,} at least one of ^R A251 ^~ R ^A258 is between ^{P 1} in the formula (1-1) It may be a binding site, and * independently represents a binding site with another structure.

Among these, from the viewpoint of solvent solubility, Y ¹ preferably contains a structure represented by any of the formulas (A2-1) to (A2-4), and is preferably the formula (A2-2) or the formula (A2-2). It is more preferable to include the structure represented by any one of A2-4).

Wherein ^{(A2-1) ~ (A2-5),} R A211 ~ R A214, R A221 ~ R A224, R A231 ~ R A238, R A241 ~ R A248 and ^R A251 ^{~ R A258,} the above equation (1 1) free of attachment to the carbonyl group in at ^least one of R A211 ^{~ R A214,} at least one of R a 221 ^{~ R A224,} at least one of ^{R A231 ~ R A238, R A241} ~ at least one of R ^{A248, and,} at least one of ^R A251 ^~ R ^A258 may be binding sites for ^{P 1} in formula (1-1).
Wherein ^(A2-1), if ^R A211 ^~ R ^A214 is not binding site of ^{P 1, R} A211 ^~ R ^A214 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 3 to 12 carbon atoms It is preferable to represent a cyclic alkyl group, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom. From the viewpoint of solvent solubility, hydrogen is used. Atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkyl halide groups having 1 to 3 carbon atoms are more preferable, and hydrogen atoms or alkyl groups having 1 to 6 carbon atoms are more preferable.
Halogen atom in the halogenated alkyl group in the R ^{A211 ~} R ^A214, or, as the halogen atom, fluorine atom, chlorine atom, bromine atom, and an iodine atom, a chlorine atom or a bromine atom.
Wherein ^{(A2-2), R A221 ~ R} A224 have the same meanings as ^R A211 ^{~ R A214} in formula (A2-1), preferable embodiments thereof are also the same.
Wherein ^{(A2-3), R A231 ~ R} A238 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, hydroxy It is preferable to represent a group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. An alkoxy group of 6 or an alkyl halide group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
Halogen atom in the halogenated alkyl group in the R ^{A231 ~} R ^A238, or, as the halogen atom, fluorine atom, chlorine atom, bromine atom, and an iodine atom, a chlorine atom or a bromine atom.
In the formula (A2-3), ^LA231 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, —O—, —S. -, -NR ^N- , a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms is preferable, and a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group. Is preferable, and it is more preferable to represent a single bond or —O—.
The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
The divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but may be a divalent aromatic hydrocarbon. It is preferably a group.
As the heterocyclic group, for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a pyrrolidine ring, More preferably, a group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, or a morpholin ring. These heterocycles may further form a fused ring with another heterocycle or a hydrocarbon ring.
The number of ring members of the heterocycle is preferably 5 to 10, and more preferably 5 or 6.
The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.
Wherein ^{(A2-4), R A241 ~ R} A248, L A241 have the same meanings as ^{R A231 ~ R A238, L} A231 in formula (A2-3), preferable embodiments thereof are also the same.
Wherein ^{(A2-5), R A251 ~ R} A258 have the same meanings as ^R A211 ^{~ R A214} in formula (A2-1), preferable embodiments thereof are also the same.

In formula ^(A2-1), at least one of ^R A211 ^~ R ^A214, is preferably a binding site for ^{P 1} in formula ^(1-1), one of the P of the ^R A211 ^~ R ^A214 more preferably a binding site with ^1, it is preferred that R ^A213 is a bond site to the P ^1.
In formula ^(A2-2), at least one of R A 221 ^{~ R A224,} is preferably a binding site for ^{P 1} in formula ^(1-1), one of the P of the ^R A221 ^~ R ^A224 more preferably a binding site with ^1, it is preferred that R ^{a 223} is a binding site between the P ^1.
In formula ^(A2-3), at least one of ^R A231 ^~ R ^A238, is preferably a binding site for ^{P 1} in formula ^(1-1), two of ^R A231 ^~ R ^A238, the more preferably a binding site of the P ^1, bract one of ^R A231 ^~ R ^A234, more preferably two one meter of the ^R A235 ^~ R ^A238 is a binding site of the ^{P 1,} R ^A231 and two of ^{R A238,} it is particularly preferred that the binding site of the ^{P 1.}
In formula ^(A2-4), at least one of R A 241 ^{~ R A248,} is preferably a binding site for ^{P 1} in formula ^(1-1), two of ^R A241 ^~ R ^A248, the more preferably a binding site of the P ^1, bract one of ^R A241 ^~ R ^A244, more preferably two one meter of the ^R A245 ^~ R ^A248 is a binding site of the ^{P 1,} R ^A241 and two of ^{R A248,} it is particularly preferred that the binding site of the ^{P 1.}
In formula ^(A2-5), at least one of ^R A251 ^~ R ^A258, is preferably a binding site for ^{P 1} in formula ^(1-1), two of ^R A251 ^~ R ^A258, the more preferably a binding site of the P ^1, bract one of ^R A251 ^~ R ^A254, more preferably two one meter of the ^R A255 ^~ R ^A258 is a binding site of the ^{P 1,} R ^A253 and two of ^{R A257,} it is particularly preferred that the binding site of the ^{P 1.}

In the formulas (A2-1) to (A2-5), it is preferable that the two * are the * in the formula (1-1), respectively. ^{That is, it is preferable that the two nitrogen atoms to which R 111} in the formula (2) is bonded are directly bonded to the positions represented by the two * in the formulas (A2-1) to (A2-5).

Among these, Y ¹ is preferably a group represented by the following formula (Y-1) or (Y-2).

Wherein ^{(Y-1), R Y11} , R Y12, R Y13 each has the same meaning as ^{R A211, R A212} and ^{R A214} in formula (A2-1), preferable embodiments thereof are also the same.
Wherein ^(Y-2), each of ^R Y21 ^~ R ^Y26, have the same meanings as ^R A242 ^{~ R A247} in formula (A2-4), preferable embodiments thereof are also the same.
In the formula (Y-1) or the formula (Y-2), * is ^{the binding site with the two nitrogen atoms to which R 111} in the formula (2) is bonded, and # is the formula (1-1), respectively. the binding site of P ¹ in, respectively.

-P ^1-
In formula (1-1), P ¹ represents a group containing a polymerizable group.
As the polymerizable group, an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide are preferable. A group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
The number of polymerizable groups contained in P ¹ is 1 or more, preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. It is particularly preferable to have one or two, and most preferably one.

Further, P ¹ is preferably a group represented by the following formula (P-1).

In formula (P-1), L ¹ represents a single bond or m + 1 valent linking group, A ² represents a polymerizable group, m represents an integer of 1 or more, and * represents a binding site with ^{Y 1.} ..
In the formula (P-1), L ¹ is preferably a single bond, a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N- , or a group in which two or more of these are bonded, preferably a single bond. A bond, or a hydrocarbon group, an ether bond, a carbonyl group, -NR ^N- , or a group in which two or more of these are bonded is more preferable.
The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
The hydrocarbon group represented by L ^1, saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or, a group represented by a combination thereof Preferably, the number of carbon atoms More preferably, it is a saturated aliphatic hydrocarbon group of 1 to 10, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.

In formula (P-1), A ² is a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group. Groups are preferred, with (meth) acryloxy groups, (meth) acrylamide groups, epoxy groups, methylol groups or alkoxymethyl groups being more preferred.

In the formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, and 1 or 2. It is particularly preferable, and 1 is most preferable.

Further, P ¹ is preferably a group represented by the following formula (P-2) or formula (P-3).

In formula (P-2), A ² represents a polymerizable group, and * represents a binding site with ^{Y 1.}
Wherein ^{(P-2), A} 2 has the same meaning as ^{A 2} in Formula (P-1), a preferable embodiment thereof is also the same.
In the formula (P-3), A ² represents a polymerizable group, and L ² is a hydrocarbon group or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N- , or. These represent a group in which two or more are bonded, Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and * represents a binding site with ^{Y 1. RN} is as described above.
Wherein (P-3), ^{A 2} has the same meaning as ^{A 2} in Formula (P-1), a preferable embodiment thereof is also the same.
In the formula (P-3), L ² is preferably a hydrocarbon group, a (poly) alkyleneoxy group, or a group represented by a combination thereof. The hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group.
As used herein, the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group. Further, in the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
As the alkylene group, an alkylene group having 1 to 30 carbon atoms is preferable, an alkylene group having 1 to 20 carbon atoms is more preferable, and an alkylene group having 1 to 10 carbon atoms is further preferable.
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is preferable. Especially preferable.
As the alkylene group in the (poly) alkyleneoxy group, an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, an ethylene group or a propylene group is more preferable, and an ethylene group is further preferable. ..
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. preferable.
In the formula (P-3), Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferable.
In the present invention, when the description is simply "ester bond", "urethane bond", "amide bond" or the like, the direction of these bonds is not limited. For example, when Z ¹ is an ester bond, the binding site with L ^{2 in Z 1} may be a carbon atom or an oxygen atom in the ester bond.

^{R 115} in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * independently represents a binding site with another structure.

In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —CO—, —S—, —SO. _2- , And NHCO-, and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO _{2- , -CH 2-} , -C (CF ₃ ) _2- , -C (CH ₃ ) _{2-, -O-, -CO.} -, - and more preferably a divalent radical selected from the group consisting of _- S-, and SO 2.

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. A preferred range of R ¹¹⁵ has the same meaning as ^{R 115} in formula (2), and preferred ranges are also the same.

Specific examples of tetracarboxylic acid dianhydride include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-. Diphenylsulfide tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3'. , 4,4'-Diphenylmethanetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5 , 7-Naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenyl hexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5, 6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4 5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrentetracarboxylic acid dianhydride, 1,1-bis (2, 3-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and these. Examples thereof include an alkyl having 1 to 6 carbon atoms and an alkoxy derivative having 1 to 6 carbon atoms.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.

It is also preferable that at least one of R ¹¹¹ and R ^{115 has an OH group.} More specifically, ^{as R 111} , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group, ^{and it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and both contain a polymerizable group. preferable. As the polymerizable group, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like. Specific examples of the polymerizable group in the specific resin include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and a methylol. Examples include a group and an amino group. As the radically polymerizable group of the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III) and the like, and a group represented by the following formula (III) is preferable.

In formula (III), ^R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), * represents a binding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- or a polyalkyleneoxy group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butanjiyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _2- , polyalkylene oxy group, and ethylene group, propylene group, trimethylene group, -CH ₂ CH (OH) CH _2- , polyalkylene oxy group are more preferable, and polyalkylene oxy group is more preferable. Oxy groups are more preferred.
In the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Further, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ) Ethoxy group is mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the cyclic alkyl group of the monocycle include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene ring, chrysen ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysine ring, phenanthrene ring, It is a thianthrene ring, a chromen ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferred.

In formula (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, even if the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. good. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

At ^{least one of R 113} and R ¹¹⁴ may be a polar conversion group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors and the like used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened.
Equation (2-A)

In formula (2-A), A ¹ and A ² represent oxygen atoms, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently. Representing a hydrogen atom or a monovalent organic group ^{, at least one of R 113} and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.

^{A 1, A 2, R 111} , R 113 and ^{R 114} each independently have the same meaning as ^{A 1, A 2, R 111} , R 113 and ^{R 114} in formula (2), and preferred ranges are also the same ..
R ¹¹² has the same meaning as ^{R 112} in formula (5), and preferred ranges are also the same.

The polyimide precursor may contain one kind of repeating structural unit represented by the formula (2), but may also contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by the formula (2) is used. Illustrated.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern formability. A polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less.
Further, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.
As used herein, the "main chain" refers to the relatively longest bound chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other bound chains.

-Fluorine atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a fluorine atom.
The fluorine atom is preferably contained in, for example, R ¹³² in the repeating unit represented by the formula (4) described later, or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group ^{in R 132} in the repeating unit represented by 4) ^{or in R 131} in the repeating unit represented by the formula (4) described later.
The amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g.

-Silicon atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.
The silicon atom is ^{preferably contained in R 131} in the repeating unit represented by the formula (4) described later, and is organically modified (poly ^{) in R 131} in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure.
Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.

-Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have it in the side chain, but it is preferable to have it in the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is ^{preferably contained in R 132} in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later. ^{It is more preferable that R 132} in the repeating unit represented by (4) ^{or R 131} in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
Of these, ethylenically unsaturated bond, ethylene R ¹³¹ in the repeating unit represented by the preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).

Wherein ^{(IV), R 20} represents a hydrogen atom or a methyl group, a methyl group is preferable.

In formula (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, —O—CH ₂ CH (OH) CH _2- , −C (= O) O−, —O (C = O) NH−. , (Poly) alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1). ~ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.

Among these, R ²¹ is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group having two or more bonds thereof, and is X. Indicates an oxygen atom or a sulfur atom, * represents a bond site with another structure, and ● represents a bond site with an oxygen atom to which ^{R 201 in the formula (III) is bonded.}
In the formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R ²¹ having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the alkylene group of 12 or the (poly) alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In the formulas (R1) to (R3), * is synonymous with * in the formula (IV), and the preferred embodiment is also the same.
The structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.

The amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.

-Crosslinkable groups other than ethylenically unsaturated bonds-
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained ^{in R 131} in the repeating unit represented by the formula (4) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.

-Polar conversion group-
The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid value-
When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving developability. Is more preferable.
The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
When the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In the present specification, pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specified. Alternatively, the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.
Further, when the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
The phenolic hydroxy group is preferably contained ^{in, for example, R 132 in the repeating unit represented by the formula (4) described later or R 131} in the repeating unit represented by the formula (4) described later.
The amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). It is more preferable that the compound contains a repeating unit and has a polymerizable group.
Equation (4)

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
When having a polymerizable group, the polymerizable group ^{may be located at at least one of R 131} and R ¹³² , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
Equation (4-1)

In formula (4-1), R ¹³³ is a polymerizable group, and the other groups are synonymous with formula (4).
Equation (4-2)

At ^{least one of R 134} and R ¹³⁵ is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. As the divalent organic group, the same group as R ¹¹¹ in the formula (2) is exemplified, and the preferred range is also the same.
In addition, ^{examples of R 131} include diamine residues remaining after removal of the amino group of diamine. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. ^{Specific examples include the example of R 111} in the formula (2) of the polyimide precursor.

It is preferable that R ¹³¹ is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the generation of warpage during firing. A diamine residue containing two or more of an ethylene glycol chain and / or a propylene glycol chain in one molecule is more preferable, and a diamine residue containing no aromatic ring is more preferable.

Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples thereof include, but are not limited to, propoxy) propane-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propane-2-amine.

R ¹³² represents a tetravalent organic group. As the tetravalent organic group, the same group as R ¹¹⁵ in the formula (2) is exemplified, and the preferable range is also the same.
For example, ^{four conjugates of a tetravalent organic group exemplified as R 115} combine with four —C (= O) − moieties in the above formula (4) to form a fused ring.

In addition, ^{examples of R 132} include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. ^{Specific examples include the example of R 115} in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group in at least one of R ¹³¹ and R ^132. More specifically, ^{as R 131} , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above (DA-1) to (DA-18) are preferable examples. As R ¹³² , the above-mentioned (DAA-1) to (DAA-5) are more preferable examples.

It is also preferable that the polyimide has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

Further, in order to improve the storage stability of the composition, the main chain end of the polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound. preferable. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Examples thereof include aminothiophenol and 4-aminothiophenol. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.

-Imidization rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited and may be 100% or less.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near ^{1377 cm -1, which is the absorption peak derived from the imide structure.} Next, the polyimide is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain the peak intensity P2 in the vicinity of ^{1377 cm -1.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

The polyimide may include the repeating structural unit of the above formula (4), all comprising one type of R ¹³¹ or R ^132, and the above formula (4) containing two or more different types of R ¹³¹ or R ^132. May include repeating units of. Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).

The polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is a monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature. A method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal encapsulant which is a monoactive ester compound) to obtain a diester with a tetracarboxylic acid dianhydride and an alcohol, and then diamine (partly monoamine). A method of reacting in the presence of a condensing agent (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorided to diamine (partly monoamine). A polyimide precursor is obtained by using a method such as a method of reacting with a terminal encapsulant (replacement with an end-capping agent), which is completely imidized by a known imidization reaction method, or an imide in the middle. Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure, and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrix5218 (manufactured by HUNTSMAN Co., Ltd.).

The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 10,000 to 30,000. More preferred. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
Equation (3)

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. show.

In the formula (3), R ¹²³ and R ^{124 are synonymous with R 113} in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable. A dicarboxylic acid consisting of is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sverin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , Octadecandioic acid, Nonadecandioic acid, Eikosandioic acid, Heneikosandioic acid, Docosandioic acid, Tricosanedioic acid, Tetracosandioic acid, Pentacosandioic acid, Hexacosandioic acid, Heptakosandioic acid, Octakosandioic acid, Nonakosandioic acid, Tria Examples thereof include contandioic acid, hentoria-contandioic acid, dotoria-contanedioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two -COOH is more preferable.

In the formula, A is -CH _2- , _{-O-, -S-, -SO 2-} , -CO-, -NHCO-, -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- Represents a divalent group selected from the group consisting of, and * represents a binding site with another structure independently.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (2), and the preferable range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Of the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferable.

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) _2- , -CH _2- , -SO _2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, ^{it is also preferable that R 122} has a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the four * and # in total are the bonding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bonded, and} preferably R ¹²² in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R ¹²² are attached in the formula (3) ^{, And two # are the bonding sites with the nitrogen atom to which R 122} in the formula (3) is bonded, or two * are the bonding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bonded. It is more preferable that the site is a site and the two #s} are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded, and the two * are the oxygen to which ^{the R 122 in the formula (3) is bonded.} It is more preferable that it is a bond site with an atom and the ^{two #s} are bond sites with a nitrogen atom to which R 122 in the formula (3) is bonded.

In the formula (As), R ₁ is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO _2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

(In the formula (A-sc), * indicates that it binds to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (A-s), phenolic hydroxy original ortho, i.e., to have also substituent R ₃ is believed to closer the distance of the carbonyl carbon and hydroxy original amide bond, It is particularly preferable in that the effect of increasing the cyclization rate when cured at a low temperature is further enhanced.

Further, in the above formula (As), _{it is said that the fact that R 2} is an alkyl group and R ₃ is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.

Further, in the above formula (As), _{it is more preferable that R 1} is an alkylene or a substituted alkylene. Specific examples of the alkylene and the substituted alkylene according to R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH _{2- and} -CH (CH ₃ ). -, -C (CH ₃ ) ₂ -has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that an excellent polybenzoxazole precursor can be obtained.

As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, paragraph numbers 805 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A are referred to. These contents can be incorporated herein by reference.

Specific examples of the structure of the bis-aminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP2013-256506, and these contents are described in the present specification. Will be incorporated into. Of course, it goes without saying that it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.

In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group ^{having 1 to 10 carbon atoms, and R 2s} is a hydrocarbon group having 1 to 10 carbon atoms. ^Yes , at least one of R 3s, R ^4s , R ^5s , and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and to achieve both the effect of suppressing warpage and the effect of improving solvent solubility.

When a diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in a composition described later, for example. It is preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.

[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable. Further, it may be a compound represented by the following formula (X) and having a polar conversion group such as an acid-degradable group.

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
When having a polar converting group such as a polymerizable group or an acid-degradable group, the polar converting group such as a polymerizable group or an acid-degradable group ^{may be located at at least one of R 133} and R ¹³⁴ , and may be located at least one of the following. It may be located at the terminal of polybenzoxazole as shown in the formula (X-1) or the formula (X-2).
Equation (X-1)

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group. It is an organic group, and the other groups are synonymous with the formula (X).
Equation (X-2)

In the formula (X-2), R ¹³⁷ is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).

A polar converting group such as a polymerizable group or an acid-degradable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor or the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include aliphatic or aromatic groups. ^{Specific examples include the example of R 121} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 121.}

R ¹³⁴ represents a tetravalent organic group. Examples of the ^{tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 122.}
For example, ^{four conjugates of a tetravalent organic group exemplified as R 122} combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a fused ring. For example, when R ¹³⁴ is the following organic group, it forms the following structure.

Polybenzoxazole preferably has an oxazole formation rate of 85% or more, more preferably 90% or more. When the oxazole formation rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

The polybenzoxazole may comprise a repeating structural unit of formula (X), all comprising one R ¹³¹ or R ^{132 , comprising two or more different types of R 131} or R ^132. It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).

The resulting polybenzoxazole, for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R ^133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor , This can be obtained by oxazole using a known oxazole reaction method.
In the case of a dicarboxylic acid, an active ester-type dicarboxylic acid derivative that has been previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield or the like.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.

[Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.

It is also preferable to synthesize using a non-halogen catalyst without using the above-mentioned halogenating agent. As the non-halogen catalyst, a known amidation catalyst containing no halogen atom can be used without particular limitation. For example, a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples thereof include carbodiimide compounds such as salts and urea compounds. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.

-End sealant-
In order to further improve the storage stability of the composition in the method for producing a polyimide precursor, etc., a polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal the end of the resin. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol, 4-Aminostyrene and the like. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.

-Solid precipitation-
A step of precipitating a solid may be included in the production of a polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.

〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. It is more preferably 50% by mass or more, and even more preferably 50% by mass or more. The resin content in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

Further, the photosensitive resin composition of the present invention preferably contains at least two kinds of resins.
Specifically, the photosensitive resin composition of the present invention may contain two or more kinds of a specific resin and another resin described later in total, or may contain two or more kinds of a specific resin, but is specific. It is preferable to contain two or more kinds of resins.
When the photosensitive resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimide precursors having different structures derived from dianhydride (R ^{115 in the above formula (2)).} It is preferable to contain the polyimide precursor of.

<Other resins>
The composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin and the like.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, instead of a cross-linking agent (also referred to as a polymerizable compound) described later, or in addition to the polymerizable compound described later, a composition of an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value. By adding to, the coatability of the composition, the solvent resistance of the organic film, and the like can be improved.

When the composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, still more preferably 10% by mass or more. ..
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferred embodiment of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the composition. Further, it is more preferably 5% by mass or less, further preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<Compounds having a group capable of photodimerization reaction and an alkoxysilyl group>
The photosensitive resin composition of the present invention contains a group capable of a photodimerization reaction and a compound B which is a compound having an alkoxysilyl group.

[Group capable of photodimerization reaction]
The group capable of the photodimerization reaction is not particularly limited, but is preferably a group capable of the dimerization reaction by ultraviolet light.
The group capable of the photodimerization reaction is preferably a group having a cinnamoyle structure, a coumarin structure, a naphthalene structure, or an anthracene structure, and more preferably a group having a cinnamoyle structure.

Further, as the group capable of the photodimerization reaction, the group represented by the following formula (P-1) is preferable.

In formula (P-1), T ¹ and T ² independently represent a hydrogen atom or a monovalent organic group, j represents 1 or 2, and R ¹ independently represents a monovalent organic group. represents, i is an integer of 0 or more, i + j is 6 or less, * represents a binding site with another structure, when j is 2, two T ¹ is each be the same may be different, if j is 2, two T ² are may be different each be the same.
A preferred embodiment of the formula ^{(P-1), T 1} , T 2 and ^{R 1} are the same as the preferred embodiment of ^T 1, ^{T 2} and ^{R 1} in formula (1-1) described later.
In the formula (P-1), i represents an integer of 0 or more, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1. It is particularly preferable that it is 0.
In the formula (P-1), j represents 1 or 2, and is preferably 1.

Further, the compound B preferably contains a structure represented by the following formula (P-2) as a structure containing a group capable of photodimerization reaction.

In formula (P-2), T ¹ and T ² independently represent a hydrogen atom or a monovalent organic group, k represents 0 or 1, j represents 1 or 2, and R ¹ is independent. In addition, i represents a monovalent organic group, i represents an integer of 0 or more, i + j represents 6 or less, * represents a bonding site with another structure, and when j is 2, T ^{1 of 2 or more.} or different may be respectively the same, when j is 2, may be different to the 2 or more T ² may each identical, there is two k respectively identical It may or may not be different.
In the formula (P-2), ^{the preferred embodiments of T 1} , T ² , R ¹ , i, and j are the same as those preferred embodiments in the above formula (P-1).
In formula (P-2), k is 0 or 1, with 0 being more preferred.

[Alkoxysilyl group]
The alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but from the viewpoint of pattern forming property and adhesion of the cured film to the metal, the trialkoxysilyl group. Is preferable.
As the alkoxy group in the alkoxysilyl group, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is further preferable.

[Equation (1-1), Eq. (1-2)]
The compound B is preferably a compound represented by the following formula (1-1) or the following formula (1-2).
Further, the compound represented by the following formula (1-1) or the following formula (1-2) is preferably a compound corresponding to the low molecular weight compound B described later.

In formula (1-1), R ¹ independently represents a monovalent organic group, n represents an integer of 0 to 5, and T ¹ and T ² independently represent a hydrogen atom or a monovalent organic. A group is represented, X ¹ represents a divalent linking group, and Z ¹ represents an alkoxysilyl group.
In formula (1-2), R ¹ independently represents a monovalent organic group, m represents an integer of 0 to 4, and T ³ to T ⁶ independently represent a hydrogen atom or a monovalent organic. Representing a group, X ² and X ³ each independently represent a divalent linking group, and Z ² and Z ³ each independently represent an alkoxysilyl group.

In the formula (1-1), R ¹ independently represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom. When R ¹ represents a monovalent organic group, a hydrocarbon group is preferable, and an alkyl group having 1 to 12 carbon atoms, a phenyl group or a biphenyl group is more preferable.
The above hydrocarbon group may be substituted with a known substituent. Examples of the substituent include a halogen atom and a cyano group.
In the formula (1-1), n represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 0.
Further, when n is 1, it is preferable that R ¹ exists at the para position with respect to the carbon atom to which T ^{1 is bonded.}
In the formula (1-1), T ¹ and T ² independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, a cyano group or a halogen atom, and more preferably a hydrogen atom. preferable.
Further ^{, an embodiment in which both T 1} and T ² are hydrogen atoms, or an embodiment in which T ¹ is a hydrogen atom and T ² is a cyano group or a halogen atom is also one of the preferred embodiments.
In the formula (1-1), X ¹ represents a divalent linking group, which is a hydrocarbon group or a hydrocarbon group, and -O-, -S-, -C (= O)-, -S (=). O) A group represented by a bond with at least one group selected from the group consisting of _2- and -NR ^{N- is preferable.}
The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
Further ^{, the embodiment in which X 1} is a group represented by the following formula (X-1) is also one of the preferred embodiments.

Wherein ^{(X1), L X1} represents a single bond or a divalent linking group, ^{A X} is -O- or -NR ^N - ^{represents, L X2} represents a divalent linking group, * has the formula In (1-1), T ¹ represents a binding site with a bonded carbon atom, and # represents a binding site with Z ¹ in the formula (1-1).
The above ^RN is as described above.
In formula (X-1), ^LX1 is preferably a single bond or a hydrocarbon group, more preferably a single bond or an optionally substituted ethylene group, and is a single bond or an unsubstituted ethylene group. It is more preferable to have.
Examples of the substituent in the ethylene group include a cyano group and a halogen atom.
Wherein ^{(X-1), A} X is -NR ^N - are preferred, -NH- is more preferable.
In formula (X-1), ^LX2 is a hydrocarbon group or a hydrocarbon group, -O-, -S-, -C (= O)-, -S (= O) _2- and -NR ^N. -A group represented by a bond with at least one group selected from the group consisting of is preferable, a hydrocarbon group is more preferable, and an alkylene group is further preferable. The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms.
In the formula (1-1), ^{the preferred embodiment of Z 1 is the same as} the preferred embodiment of the alkoxysilyl group in the above-mentioned compound B.

In the formula (1-2), ^{the preferred embodiment of R 1 is the same as} the preferred embodiment of the formula (1-1).
In the formula (1-2), T ³ to T ⁶ independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, a cyano group or a halogen atom, and more preferably a hydrogen atom. preferable.
Further ^{, an embodiment in which both T 1} and T ² are hydrogen atoms, or an embodiment in which T ⁴ and T ⁵ are hydrogen atoms and T ³ and T ⁶ are cyano groups or halogen atoms is also a preferred embodiment. It is one.
In formula (1-2), X ² and X ³ each independently represent a divalent linking group, and are a hydrocarbon group or a hydrocarbon group, and —O—, —S—, —C (= O). )-, -S (= O) ₂ -and-NR ^N- are preferred groups represented by binding to at least one group selected from the group.
The above ^RN is as described above.
In the formula (1-2) ^{, an embodiment in which one or both of X 2} and X ³ are the groups represented by the above formula (X-1) is also a preferred embodiment.
However, when X ² is a group represented by the above formula (X-1), * in the formula (X-1) is a bond with the carbon atom to which ^{T 3 in the formula (1-2) is bonded.} A site is represented, and # represents a binding site with ^{Z 2 in the formula (1-2).}
Further, when X ³ is a group represented by the above formula (X-1), * in the formula (X-1) is a carbon atom to which ^{T 6 is bonded in the formula (1-2).} The # represents the binding site, and # represents the binding site with Z ³ in the formula (1-2).
In the formula (1-2), ^{the preferred embodiments of Z 2} and Z ³ are the same as the preferred embodiments of the alkoxysilyl group in the above-mentioned compound B, respectively.

[Azole group]
It is also preferable that the compound B contains an azole group.
According to the above aspect, it is considered that the adhesion of the cured film to the metal is further improved by coordinating the azole group with a metal such as copper.
The azole group in compound B is a complex 5-membered ring compound containing one or more nitrogen atoms as a ring member, and has one hydrogen atom from the complex 5-membered ring compound which may have a substituent or a fused ring structure. It may be a group having a structure excluding one or more, but it may be a complex 5-membered ring compound containing only one or more nitrogen atoms and one or a plurality of carbon atoms as a ring member, and may have a substituent. It is preferable that the group has a structure in which one or more hydrogen atoms are removed from the complex 5-membered ring compound.
From the viewpoint of adhesion of the cured film to the metal, the azole groups include a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, and a 1,2,4-triazole ring. , A benzotriazole ring, or a group having a structure in which one or more hydrogen atoms are removed from the tetrazole ring, preferably from an imidazole ring, a benzimidazole ring, 1,2,4-triazole ring, or a benzotriazole ring. It is more preferable that the group has a structure excluding one or more hydrogen atoms.

Further, the azole group in compound B is preferably a group represented by the following formula (B-1) or the following formula (B-2).

In formula (B-1), ^RB1 represents a binding site with another structure, a hydrogen atom or a monovalent organic group, and Z ^B1 to Z ^B4 independently represent = CR ^B7 -or a nitrogen atom. R ^B7 represents a binding site, a hydrogen atom or a monovalent organic group with other structures, of R ^B1 and R ^B7 contained in the formula (B1), the binding site of the at least one other structure Represents;
In formula (B-2), ^RB2 to ^RB6 independently represent a bond site with another structure, a hydrogen atom or a monovalent organic group, and Z ^B5 and Z ^B6 independently represent = CR ^B8. - or a nitrogen ^atom, the binding site of the ^{R B8} other structures, represent a hydrogen atom or a monovalent organic group, of ^R B2 ^{~ R B6} and ^{R B8} included in the formula (B2), at least One represents a binding site with another structure.

In the formula (B-1), ^RB1 represents a binding site with another structure, a hydrogen atom or a monovalent organic group, and is more preferably a binding site with another structure.
The monovalent organic group represented by R ^B1, not particularly limited, but as long as the effect of the present invention are obtained can be used known organic group, a hydrocarbon group or an amino group It is preferably an alkyl group or an amino group, more preferably. The number of carbon atoms of the hydrocarbon group or the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 4.
The amino group may be a substituted amino group or an unsubstituted amino group.

In formula (B-1), Z ^B1 to Z ^B4 independently represent = CR ^B7 − or a nitrogen atom.
Among ^{them, two of Z B1} to Z ^B4 are nitrogen atoms and two are = CR ^B7- , and one of Z ^B1 to Z ^B4 is a nitrogen atom and three are = CR ^B7- . Alternatively, it is preferable that ^{three of Z B1} to Z ^B4 are nitrogen atoms and one is = CR ^{B7 −.}
Among these, Z ^B1 and Z ^B3 are nitrogen atoms, Z ^B2 and Z ^B4 are = CR ^B7 −, Z ^B1 and Z ^B2 are nitrogen atoms, and Z ^B3 and Z ^B4 are = CR. ^B7 -in which Z ^B2 is a nitrogen atom and Z ^B1 , Z ^B3 and Z ^B4 are = CR ^B7 -or in which Z ^B1 , Z ^B2 and Z ^B3 are nitrogen atoms and Z ^B4 is. The embodiment in which = CR ^B7 − is preferable, and the embodiment in which Z ^B1 and Z ^B3 are nitrogen atoms and Z ^B2 and Z ^B4 are = CR ^B7 − is more preferable.
The ^RB7 is preferably a hydrogen atom or a monovalent organic group.
Further, when Z ^B1 , Z ^B2 and Z ^B3 are nitrogen atoms and Z ^B4 is = CR ^B7 −, ^RB7 is preferably a binding site with another structure.
A preferred embodiment of the monovalent organic group in R ^B7 is similar to the preferred embodiment of the monovalent organic group in the above R ^B1.

Of R ^B1 and R ^B7 contained in the formula (B1), at least one represents a bonding site with the other structures, it is preferable that at least R ^B1 represents a binding site with another structure. Further, in the equation (B1), only the R ^B1 represents a binding site with another structure, embodiments each represent R ^B7 independently a hydrogen atom or a monovalent organic group, preferred embodiments of the present invention 1 It is one.

In formula (B-2), Z ^B5 and Z ^B6 each independently ^{represent = CR B8} -or a nitrogen atom.
Above ^all, aspects represents the ^{Z B5} and ^{Z B6} are both nitrogen atom, ^or, the ^{Z B5} nitrogen ^{atom, Z B6} is = ^{CR B8} - aspects that represent each desirable.
In formula ^(B-2), when ^{Z B5} and ^{Z B6} is representative of the either nitrogen ^atom, it is preferred ^{that R B6} represents a binding site with another structure. Further, in the formula (B-2), ^{a mode in which both Z B5} and Z ^B6 represent a nitrogen atom and ^{only RB6} represents a binding site with another structure is also one of the preferred embodiments of the present invention. be.
In formula ^(B-2), the ^{Z B5} nitrogen ^{atom, Z B6} is = ^{CR B8} - If the representative ^{respectively,} it is preferred ^{that R B8} represents a binding site with another structure. Further, in the formula (B-2), it ^{is also preferable that Z B5} represents a nitrogen atom, Z ^B6 represents = CR ^B8 −, and ^{only RB8} represents a binding site with another structure. It is one of the embodiments.

In the formula (B-2), ^{it is preferable that RB2} to ^RB5 each independently represent a hydrogen atom or a monovalent organic group. A preferred embodiment of the monovalent organic group in R ^B2 ~ ^{R B5} is the same as the preferred embodiment of the monovalent organic group in the above ^{R B1.}
In formula ^(B-2), the ^{Z B5} nitrogen ^{atom, Z B6} is = ^{CR B8} - If the representative ^{respectively, R B6} preferably represents a hydrogen atom or a monovalent organic group. A preferred embodiment of the monovalent organic group in R ^B6 are the same as the preferred embodiment of the monovalent organic group in the above R ^B1.
In other cases, ^RB6 preferably represents a binding site with another structure. In ^particular, the ^{Z B5} nitrogen ^{atom, Z B6} is = ^{CR B8} - If the representative ^{respectively,} it is preferred ^{that R B8} represents a binding site with another structure.
In formula (B-2), ^RB8 preferably represents a binding site with another structure.
Z ^B5 and Z ^B6 are both = CR B8 ^- When referring to, one of R ^B8 represents a binding site with another structure, it is preferable that the other represents a hydrogen atom or a monovalent organic group. A preferred embodiment of the monovalent organic group in R ^B8 are the same as the preferred embodiment of the monovalent organic group in the above R ^B1.

Of ^R B2 ^{~ R B6} and ^{R B8} included in the formula (B2), at least one represents a binding site with another structure, at least ^{R B6} or ^{R B8} represents a binding site with another structure Is preferable. Further, in the formula (B-2), ^{only one of RB6} and ^RB8 represents a binding site with another structure, and the other of ^RB6 and ^RB8 and ^RB2 to ^RB5 are independently hydrogen atoms. Alternatively, an embodiment representing a monovalent organic group is also one of the preferred embodiments of the present invention.

Among these, the azole group is preferably a group represented by any of the following formulas (B-3) to (B-6).

In formulas (B-3) to (B-6), ^RB9 to ^RB20 each independently represent a hydrogen atom or a monovalent organic group, and * represents a binding site with another structure.
In formulas (B-3) to (B-6), ^RB9 to ^RB20 are preferably hydrocarbon groups, amino groups, or nitro groups.
Wherein (B-3) ~ formula ^(B-6), preferred embodiments of the hydrocarbon group for R B9 ^{~ R B20} are the same as the preferred embodiment of the hydrocarbon group in the above ^{R B1.}
Further, ^{the amino group in RB9} to ^RB20 may be a substituted amino group or an unsubstituted amino group.

The compound B may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as “low molecular weight compound B”) or a resin (hereinafter, also referred to as “resin B”).
Further, from the viewpoint of the adhesion of the cured film to the metal, it is also preferable that the photosensitive resin composition contains both the low molecular weight compound B and the resin B.
From the viewpoint of adhesion, the compound B is preferably a resin.

[Low molecular weight compound B]
The molecular weight of the low molecular weight compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

The number of groups capable of photodimerization reaction in the low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.
The number of alkoxysilyl groups in the low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

The low molecular weight compound B is preferably a compound represented by the above formula (1-1) or formula (1-2).

[Resin B]
The weight average molecular weight of the resin B is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000.

The molar amount of the photodimerizable group in 1 g of the resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and 0.005 to 0. It is more preferably 1 mmol / g.

The molar amount of the alkoxysilyl group in 1 g of the resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and 0.005 to 0.1 mmol / g. It is more preferably g.

The resin B is a resin having a repeating unit containing a photodimrification-reactive group and a repeating unit containing an alkoxysilyl group, or a resin having a repeating unit containing a photodimrification-reactive group and an alkoxysilyl group. It is more preferable that the resin has a repeating unit containing a group capable of photodimerization reaction and a repeating unit containing an alkoxysilyl group.

-Repeating unit containing groups capable of photodimerization reaction-
The resin B preferably contains a repeating unit represented by the following formula (BL-1) as a repeating unit containing a group capable of photodimerization reaction.

In formula (BL-1), L ^L1 represents a single bond or a divalent linking group, XL1 represents a ^{photodiquantifying} reactive group, and R represents a hydrogen atom or a methyl group.
In the formula (BL-1), L ^L1 represents a single bond or a divalent linking group, and a divalent linking group is preferable.
The above-mentioned divalent linking group includes a hydrocarbon group or a hydrocarbon group, and -O-, -S-, -C (= O)-, -S (= O) _2- and -NR ^N-. A group represented by a bond with at least one group selected from the group is preferable, and a hydrocarbon group is more preferable.
The above ^RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
Among these, ^LL1 is preferably a group represented by the following formula (BL-1-1).

In formula (BL-1-1), L ^L4 represents a divalent linking group, L ^L5 represents a single bond or a divalent linking group, and * represents a bond with a carbonyl group in formula (BL-1). represents ^{sites, a L1} and ^{a L2} is -O- or -NR ^N - represents, # represents the bonding site with ^{X L1} in (BL-1).
^RN is as described above.

In the formula (BL-1-1), L ^L4 is a hydrocarbon group or a hydrocarbon group, and -O-, -S-, -C (= O)-, -S (= O) _2-and-. A group represented by a bond with at least one group selected from the group consisting of NR ^{N − is preferable, and a hydrocarbon group is more preferable.}
The above ^RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

In the formula (BL-1-1), L ^L5 is preferably a single bond. ^{The preferred embodiment when LL5} is a divalent linking group is the same as the preferred embodiment of ^LL4 described above.

In the formula (BL-1-1), A ^L1 and A ^{L 2} represent -O- or -NR ^N-, and are preferably -O-.

In the formula (BL-1), ^{the preferred embodiment of XL1 is the same as} the preferred embodiment of the photodimerizable group in the above-mentioned compound B.

-Repeating unit containing alkoxysilyl group-
The resin B preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing an alkoxysilyl group.

Wherein (BA-2), ^{A 3} is -O- or -NR ^N - ^{represents, L P1} represents a divalent linking ^{group, X P1} represents an alkoxysilyl group, R represents a hydrogen atom or a methyl group show.

Wherein (BA-2), ^{A 3} is -O- or -NR ^N - represents, -O- it is preferable. ^RN is as described above.

In the formula (BA-2), ^LP1 represents a divalent linking group, which is a hydrocarbon group or a hydrocarbon group, and —O—, —S—, —C (= O) −, —S (=). O) A group represented by a bond with at least one group selected from the group consisting of _2- and -NR ^{N- is preferable, and a hydrocarbon group is more preferable.}
The above ^RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

In the formula (BA-2), ^{the preferred embodiment of XP1 is the same as} the preferred embodiment of the alkoxysilyl group in the above-mentioned compound B.

-Repeating unit containing azole group-
The resin B preferably contains a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group.

In formula (BA-1), L ³ represents a single bond or a divalent linking group, X ³ represents an azole group, and R represents a hydrogen atom or a methyl group.
In formula (BA-1), L ³ represents a single bond or a divalent linking group.
The above-mentioned divalent linking group includes a hydrocarbon group or a hydrocarbon group, and -O-, -S-, -C (= O)-, -S (= O) _2- and -NR ^N-. A group represented by a bond with at least one group selected from the group is preferable, and a hydrocarbon group is more preferable.
The above ^RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
Among these, ^{L 3} is a single bond, preferably a group represented by the following formula (BA-1-1) a group or the following formula represented (BA-1-2).

In formula (BA-1-1) or formula (BA-1-2), L ⁴ represents a divalent linking group, L ⁵ represents a single-bonded or divalent linking group, and L ⁶ represents a divalent linking group. Representing a linking group, L ⁷ represents a single bond or a divalent linking group, * represents a bonding site with a carbonyl group in the formula (BA-1), and A ¹ and A ² represent -O- or -NR. ^It represents N −, and # represents the binding site with ^{X 3} in (BA-1).

In the formula (BA-1-1), L ⁴ is a hydrocarbon group or a hydrocarbon group, and -O-, -S-, -C (= O)-, -S (= O) _2-and-. A group represented by a bond with at least one group selected from the group consisting of NR ^{N − is preferable, and a hydrocarbon group is more preferable.}
The above ^RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

Wherein (BA-1-1), it is preferred that ^{L 5} represents a single bond. When L ⁵ is a divalent linking group, L ⁵ is a hydrocarbon group or a hydrocarbon group and -O-, -S-, -C (= O)-, -S (= O) _2- A group represented by a bond with at least one group selected from the group consisting of and -NR ^{N- is preferable, and a hydrocarbon group is more preferable.}

In the formula (BA-1-2), L ^{6 is synonymous with L 4} in the formula (BA-1-1), and the preferred embodiment is also the same.

In formula (BA-1-2), L ⁷ is preferably a divalent linking group. When L ⁷ is a divalent linking group, ^{the preferred embodiment of L 7} is the same as the preferred embodiment when ^{L 5} is a divalent linking group in the above formula (BA-1-1).

In the formula (BA-1-1) or the formula (BA-1-2), A ¹ and A ² represent -O- or -NR ^N- , and -O- is preferable. ^RN is as described above.

Wherein (BA-1), preferred embodiments of the azole group in ^{X 3} are as described above. Binding sites with other structures in the azole group described above, corresponds to the binding site of the L ³ in the formula (BA-1).

The resin B may contain only one type of repeating unit represented by the formula (BA-1), or may contain two or more types.
When the resin B contains a repeating unit containing an azole group, the molar content of the azole group in 1 g of the resin B is preferably 0.001 to 5 mmol / g, and preferably 0.01 to 1 mmol / g. More preferred.

-Other repeating units-
Further, the resin B may further have another repeating unit different from the repeating unit represented by the above formula (BL-1), formula (BA-2) or formula (BA-1).

〔Concrete example〕
Specific examples of the compound B include, but are not limited to, the compounds used in the examples.

〔Content〕
The content of compound B is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and 0, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably .15 to 2% by mass.
The photosensitive resin composition of the present invention may contain only one kind of compound B, or may contain two or more kinds of compound B. When two or more kinds of compound B are contained, the total amount is preferably in the above range.

<A compound that does not have at least one of a photodimerizable group and an alkoxysilyl group and has an azole group>
From the viewpoint of the adhesion of the obtained cured film to the metal, the photosensitive resin composition of the present invention does not have at least one of a photodimerizable group and an alkoxysilyl group, and has an azole group. It preferably contains compound C, which is a compound.
The photosensitive resin composition of the present invention may contain a compound (hereinafter, also referred to as "Compound C1") having neither a photodimrification reaction group nor an alkoxysilyl group and having an azole group. preferable.
Further, the photosensitive resin composition of the present invention preferably contains a compound having no alkoxysilyl group, capable of photodimerization reaction, and an azole group (hereinafter, also referred to as "Compound C2"). ..
Further, an embodiment containing both compound C1 and compound C2 is also one of the preferred embodiments of the present invention.
Further, the photosensitive resin composition of the present invention may contain a compound having an alkoxysilyl group and an azole group without having a group capable of photodimerization reaction.

The preferred embodiments of the photodimerizable group, the alkoxysilyl group, and the azole group in the compound C are the same as the preferred embodiments of the respective groups in the compound having the photodimerizable group and the alkoxysilyl group described above. Is.

[Compound C1]
The compound C1 is preferably a compound represented by the following formula (C-1) or the following formula (C-2).

Wherein ^(C-1), respectively Z 1 ~ ^{Z 4} are independently, = CR ⁷ - or a nitrogen atom, ^{R 1} represents a hydrogen atom or a monovalent organic group, ^{R 7} is a hydrogen atom or a monovalent The organic group represented by the formula (C-1) does not include a photodimerizable group and an alkoxysilyl group;
Wherein ^(C-2), the Z 5 ~ ^{Z 6} are each independently, = CR ⁸ - or a nitrogen ^atom, are each R 2 ~ ^{R 6} independently represent a hydrogen atom or a monovalent organic radical, R ^{Reference numeral 8} represents a hydrogen atom or a monovalent organic group, and the structure represented by the formula (C-2) does not include a group capable of photodimerization reaction and an alkoxysilyl group.

In formula (C-1), Z ¹ to Z ⁴ independently represent = CR ⁷ − or a nitrogen atom.
Among ^them, one is a nitrogen atom of Z 1 ~ ^{Z 4,} 3 one is = CR ⁷ - aspects ^is, two of Z 1 ~ ^{Z 4} is a nitrogen atom, two are = CR ⁷ - in which embodiment, Alternatively, it is preferable that ^{three of Z 1} to Z ⁴ are nitrogen atoms and one is = CR ^{7 −.}
Further, among these, are ^{Z 1} and ^{Z 3} is a nitrogen atom, ^{Z 2} and ^{Z 4} is = CR ⁷ - embodiment is a ^{Z 1} and ^{Z 2} is a nitrogen atom, ^{Z 3} and ^{Z 4} is = CR ^7- or a mode in which Z ¹ , Z ² and Z ³ are nitrogen atoms and Z ⁴ is = CR ⁷ -is preferable, Z ¹ and Z ³ are nitrogen atoms, and Z ² and Z are ^It is more preferable that 4 is = CR ^B7 −, or Z ¹ , Z ² and Z ³ are nitrogen atoms and Z ⁴ is = CR ^{7 −.}

In the formula (C-1), R ¹ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
The hydrocarbon group or the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.

In the formula (C-1), the preferred embodiment of R ⁷ is the same as that ^{of R 1.}

Wherein (C-2), the ^{Z 5} and ^{Z 6} are each independently, = CR ⁸ - represents a group or a nitrogen atom.
Above all, aspects ^{Z 5} and ^{Z 6} represent both nitrogen atoms, or a ^{Z 5} is a nitrogen atom, ^{Z 6} is = CR ⁸ - aspects that represent each desirable.

In the formula (C-2), R ² to R ⁶ and R ⁸ are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and a hydrogen atom. Is particularly preferable.

[Compound C2]
The photosensitive resin composition of the present invention preferably contains a compound (compound C2) having no alkoxysilyl group, a group capable of photodimerization reaction, and an azole group.
The compound C2 is preferably a compound represented by the following formula (DA-1).

Wherein ^{(DA-1), X D1} represents a photo-dimerization reaction ^{groups, X D2} represents an azole group, n represents an integer of 1 or more, m represents an integer of 1 or more, ^{L D} is n + m Represents a valence organic group.
Wherein (DA-1), similarly to the preferred embodiment of the preferred embodiment described above the photo-dimerization reaction groups and photo-dimerization reaction groups in the compound having an alkoxysilyl group photo-dimerization reaction groups in X ^D1 Is. In particular, ^{L D} is preferably a group represented by the formula (P-1).
Wherein (DA-1), preferred embodiments of the azole group in X ^D2 the above photo-dimerization reaction groups, and the same as the preferred embodiment of the azole group in the compound having an alkoxysilyl group.
In the formula (DA-1), n is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (DA-1), m is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
Wherein (DA-1), ^{L D} is a hydrocarbon group or a hydrocarbon group, -O -, - S -, - C (= O) -, - S (= O) 2 - and -NR ^N -Preferably, a group represented by a bond with at least one group selected from the group consisting of.
The above ^RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

The compound represented by the formula (DA-1) is preferably a compound represented by the following formula (DA-2).

In formula (DA-2), X ^D1 represents a ^{photodimerizable group, X D2} represents an azole group, LD ¹ represents a single bond or a divalent linking group, and LD ² represents a single bond or a divalent group. Represents a linking group of.
A preferred embodiment of formula ^{(DA-2), X D1} and ^{X D2} are the same as the preferred embodiment of the ^{X D1} and ^{X D2} in the formula (DA-1).
In formula (DA-2), ^LD1 is preferably a single bond or a hydrocarbon group, more preferably a single bond or an optionally substituted ethylene group, and is a single bond or an unsubstituted ethylene group. It is more preferable to have a single bond, and it is particularly preferable to have a single bond.
Examples of the substituent in the ethylene group include a cyano group and a halogen atom.
Wherein ^{(DA-2), L D2} is a single bond, or is preferably a group represented by the following formula (LD2).

In the formula (LD2), ^AD is —O— or −NR ^N− , preferably ^{−NR N−.}
The above ^RN is as described above.
In the formula (LD2), ^LD3 is a divalent linking group, preferably a hydrocarbon group, and more preferably an alkyl group. The hydrocarbon group or the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
In the formula (LD2), * represents a binding site with a carbonyl group in the formula (DA-2), and # represents a binding site with ^{X D2 in the formula (DA-2).}

〔resin〕
The compound C may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as “low molecular weight compound C”) or a resin (hereinafter, also referred to as “resin C”).
Further, from the viewpoint of the adhesion of the cured film to the metal, it is also preferable that the photosensitive resin composition contains both the low molecular weight compound C and the resin C.
From the viewpoint of adhesion, the compound C is preferably a resin.
Further, the above-mentioned compound C1 is preferably a compound corresponding to the low molecular weight compound C.
The above-mentioned compound C2 is preferably a resin.
Further, an embodiment in which the compound C2 includes the compound C2 corresponding to the low molecular weight compound C and the compound C2 corresponding to the resin C is also one of the preferred embodiments of the present invention.

[Low molecular weight compound C]
The molecular weight of the low molecular weight compound C is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

The number of azole groups in the low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.
When the low molecular weight compound C contains a group capable of photodimerization reaction, the number of groups capable of photodimerification reaction is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. preferable.

When the low-molecular-weight compound C corresponds to the above-mentioned compound C1, the low-molecular-weight compound C is preferably a compound represented by the above-mentioned formula (C-1) or (C-2).
When the low-molecular-weight compound C corresponds to the above-mentioned compound C2, the low-molecular-weight compound C is preferably a compound represented by the above-mentioned formula (DA-1), and is preferably a compound represented by the above-mentioned formula (DA-2). It is more preferable to have.

[Resin C]
The weight average molecular weight of the resin C is preferably 3000 to 100,000, more preferably 3000 to 50,000, and even more preferably 5000 to 30,000.

The resin C is preferably a resin having a repeating unit containing an azole group.
Further, the resin C is more preferably a resin having a repeating unit containing an azole group and a repeating unit containing a group capable of photodimerization reaction.
The preferred embodiment of the repeating unit containing an azole group and the repeating unit containing a photodiquantifying reactive group is the same as the preferred embodiment of these repeating units in the resin B described above.

The molar amount of the azole group in 1 g of the resin C is preferably 0.001 to 15 mmol / g, more preferably 0.01 to 10 mmol / g, and preferably 0.1 to 5 mmol / g. More preferred.

When the resin C contains a photodimerizable group, the molar amount of the photodimerizable group in 1 g of the resin C is preferably 0.001 to 15 mmol / g, preferably 0.01 to 10 mmol / g. It is more preferably 0.1 to 5 mmol / g, and even more preferably 0.1 to 5 mmol / g.

Resin C may further have other repeating units. Examples of other repeating units include repeating units having a polymerizable group.

〔Concrete example〕
Specific examples of the compound C include, but are not limited to, the compounds used in the examples.

〔Content〕
The content of compound C is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and 0, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably .15 to 2% by mass.
The photosensitive resin composition of the present invention may contain only one kind of compound C, or may contain two or more kinds of compound C. When two or more kinds of compound C are contained, the total amount is preferably in the above range.

<Solvent>
The photosensitive resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.

Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples thereof include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.

As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.

As the sulfoxides, for example, dimethyl sulfoxide is preferable.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Suitable examples include dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

As ureas, N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.

Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

The solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Further, a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferable.

Among these, the photosensitive resin composition of the present invention preferably contains esters, and more preferably contains a lactone-based solvent.
The lactone-based solvent refers to a solvent containing a lactone structure, and examples thereof include γ-butyrolactone, ε-caprolactone, and δ-valerolactone.
The content of the lactone-based solvent with respect to the total mass of the solvent is not particularly limited, but is preferably 30 to 100% by mass, more preferably 40 to 95% by mass, and more preferably 50 to 90% by mass. More preferred.

From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The solvent may be contained in only one kind, or may be contained in two or more kinds. When two or more kinds of solvents are contained, the total is preferably in the above range.

<Photosensitizer>
The composition of the present invention preferably contains a photosensitive agent.
As the photosensitive agent, a photopolymerization initiator is preferable.

[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as the photosensitive agent.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
Further, as the photoradical polymerization initiator, the oxime compound described later is preferable.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient ^{of at least about 50 L · mol -1} · cm ^-1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

A known compound can be arbitrarily used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, it becomes possible to improve the exposure latitude more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = N—O—C (= O)-in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA ARCULDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Further, an oxime compound having the following structure can also be used.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of Japanese Patent Publication No. 164471.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

Further preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and an oxime compound is further preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms. 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or biphenyl, R ^I01 is a group represented by formula (II), the same as R ^I00 The groups, R ^I02 to R I ^04, are each independently an alkyl having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

In the formula, R ^I05 to R ^I07 are the same as ^{R I 02} to R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.

[Photoacid generator]
Further, it is also preferable that the composition of the present invention contains a photoacid generator as a photosensitive agent.
By containing the photoacid generator, for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is formed by the developing solution. A positive pattern to be removed can be obtained.
Further, when the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed portion promotes the crosslinking reaction of the polymerizable compound. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion. According to such an embodiment, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate.

The quinone-diazide compound includes a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide sulfonic acid is ester-bonded and a sulfonamide bond. Examples include those bonded by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, as the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazido sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.

Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).

Wherein (OS-1), ^{X 3} is an alkyl group, an alkoxyl group, or a halogen atom. If X ³ there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X ³ may have a substituent. The alkyl group in the above X ^3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X ^3, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X ^3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different.
In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.

Wherein (OS-1), m3 is 3, ^{X 3} is a methyl group, the substitution position of ^{X 3} is ^{ortho, R 34} is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and R ^{s2, which may be present in a plurality of R s2,} independently represents a hydrogen atom, an alkyl group and an aryl group. ^{R s6} , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), ^{an alkyl group represented by R s1} (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.

In the formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. ^{Of the Rs2} that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by ^{R s2 may have a substituent T.}
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In the formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In the formulas (OS-103) to (OS-105), the ^{alkyl group represented by R s6} (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituted groups. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.

Further, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111). The compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R ^t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R ^t2 represents a hydrogen atom or a methyl group.
In the formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, and a phenyl group. Alternatively, it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.

In the formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.

Other suitable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In the formula (OS-101) or the formula (OS-102), ^Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, and the like. Represents an aryl group or a heteroaryl group. The ^{embodiment in which R u9} is a cyano group or an aryl group is more preferable, and the embodiment in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), ^Ru2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, ^-NH- , -NR u5-, -CH _2- , -CR ^u6 H- or CR ^u6 R ^u7. -, R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In the formula (OS-101) or the formula (OS-102), ^Ru1 to ^Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the ^{R u1} ~ R ^u4. At this time, the ring may be condensed to form a fused ring together with the benzene ring. The R ^u1 ~ ^{R u4,} a hydrogen atom, preferably a halogen atom or an alkyl group, ^also aspects to form the at least two aryl groups bonded to each other of R u1 ^{~ R u4} preferred. Above all, it is preferable that all of ^Ru1 to ^{Ru4 are hydrogen atoms.} Any of the above-mentioned substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.

In addition, a commercially available product may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-690 (any of which). Also Fujifilm Wako Pure Chemical Industries, Ltd., Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF). (Made by Midori Chemical Industries, Ltd.) and the like.

Further, a compound represented by the following structural formula is also mentioned as a preferable example.

As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, JP-A-55-3207, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, JP-A-63-70243, JP-A-63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No3), (1970) and the like can be mentioned, and in particular, oxazole compounds substituted with a trihalomethyl group: S-triazine compounds can be mentioned.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example 2,4,6-tris (monochromomethyl)-. s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.

As the photoacid generator, an organic borate compound can also be applied. Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech'98. Proceeding Compound 19-22, 1998, Chicago", etc. Organic borate, organic boron sulfonium complex or organic boron oxosulfonium complex described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554. Japanese Patent Laid-Open No. 6-175553, Organic Boron Iodonium Complex, Japanese Patent Application Laid-Open No. 9-188710, Organic Boron Phosphorium Complex, Japanese Patent Application Laid-Open No. 6-348011, JP-A-7-128785, JP-A. Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.

As the photoacid generator, a disulfone compound can also be applied. Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.

Examples of the onium salt compound include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069, Phosphonium salts described in 055 and 4,069,056, European Patents 104 and 143, US Patents 339,049 and 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent. No. 4,933,377, No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, The sulfonium salt according to each specification of German Patent No. 2,904,626, 3,604,580, and 3,604,581. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. Mol. V. Crivello et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), selenonium salt, C.I. S. Wen et al, Theh, Proc. Conf. Rad. Examples thereof include onium salts such as the arsonium salt and the pyridinium salt described in Curing ASIA, p478 Tokyo, Oct (1988).

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).

In the formula (RI-I), Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 to 12 carbon atoms. 12 alkenyl groups, alkynyl groups with 1 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, allyloxy groups with 1 to 12 carbon atoms, halogen atoms, 1 to 12 carbon atoms Alkylamino group, dialkylamino group with 1 to 12 carbon atoms, alkylamide or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group with 1 to 12 carbon atoms, carbon Examples thereof include thioaryl groups having the number 1 to 12. Z11 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable. In the formula (RI-II), Ar21 and Ar22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and a preferable substituent is an alkyl group having 1 to 12 carbon atoms. , An alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, and carbon. Alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 to 12 carbon atoms Examples thereof include a thioalkyl group of 1 to 12 and a thioaryl group having 1 to 12 carbon atoms. Z21 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In the formula (RI-III), R31, R32, and R33 each represent an aryl group or an alkyl group having 20 or less carbon atoms, an alkenyl group, and an alkynyl group, which may independently have 1 to 6 substituents, and are preferable. From the viewpoint of reactivity and stability, an aryl group is desirable. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Allyloxy group with 1 to 12 carbon atoms, halogen atom, alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.

Specific examples include the following.

When the photoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.

[Photobase generator]
The photosensitive resin composition of the present invention may contain a photobase generator as the photosensitive agent.
When the photosensitive resin composition contains a photobase generator and a cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by promoting the cyclization of the specific resin by the base generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mother. , 11, 170 (1999); H. Tachi, M. et al. Shirai, and M. Tsunooka, J.M. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J.M. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H. et al. Tachi, and S. Yoshitaka, J.M. Photopolym. Sci. Technol. , 9, 13 (1996); K.K. Suyama, H. et al. Araki, M. et al. Shirai, J.M. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex or an ammonium salt, or those latent by salt formation of an amidin moiety with a carboxylic acid. Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. Can be mentioned.
In the present invention, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples of the photobase generator.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
From the viewpoint of the imidization rate, it is preferable that the basic substance has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, and more preferably 3 or more. The upper limit of the above pKa is not particularly limited, but is preferably 20 or less.
Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; You can refer to the values described in Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) shall be used as pKa.

From the viewpoint of storage stability of the photosensitive resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator is preferable. It is preferable that there is no charge on the top. As the photobase generator, it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Further, from the viewpoint of chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in the structure.

Further, for the above reasons, as the photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
Examples of the photobase generator according to the present invention include a photobase generator having a cinnamon acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122, JP-A-2006-189591. A photobase generator having a carbamate structure as disclosed in JP-A and JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581, Carbamoyl. Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.

In addition, as the photobase generator, the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication No. 2010/064631.

In addition, a commercially available product may be used as the photobase generator. Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-207, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG. -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (Made by Tokyo Chemical Industry Co., Ltd.) and the like.

When the photobase generator is contained, the content thereof is preferably 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. Is more preferable, and 2 to 15% by mass is further preferable. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, the total is preferably in the above range.

<Thermal polymerization initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be promoted in the heating step described later, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. More preferably, it is 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

<Thermal acid generator>
The composition of the present invention may contain a thermoacid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.

The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and at the time of final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane. Haloalkyl sulfonic acid such as sulfonic acid is preferable. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935.

Among them, those that generate an alkyl sulfonic acid having 1 to 4 carbon atoms or a haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonic acid (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) Methyl ((2-Methylphenyl) Methyl) Sulfonium, 3-(5-(((propylsulfonyl) Oxy) Imino) Thiophen-2 (5H) -Ilidene) -2- (o-Trill) Propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred as the thermal acid generator.

Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.

The content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 part by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.

<Onium salt>
The photosensitive resin composition of the present invention may further contain an onium salt.
In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt or phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.

Further, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the photosensitive resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermal base generator described later.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.

When the photosensitive resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Thermal base generator>
The photosensitive resin composition of the present invention may further contain a thermal base generator.
In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermal base generator.
The other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermal base generator include compounds represented by the formula (B1) or the formula (B2).

In the formula (B1) and the formula (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, ^{none of Rb 1} , Rb ² and Rb ³ has a carboxy group. In the present specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

In the formulas (B1) and (B2), ^{it is preferable that at least one of Rb 1} , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. As the single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have a substituent as long as the effect of the present invention is exhibited. Rb ¹ and Rb ² may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly linear, branched, or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. Maybe cyclohexyl groups are more preferred.

Examples of Rb ³ include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18 carbon atoms). ~ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable). Preferably, 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24). 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbon atoms are preferred). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). Among them, a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent as long as the effect of the present invention is exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as ^{Rb 1} and Rb ² in the formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), and arylalkyl groups (7 to 7 to carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.

Rb ³⁵ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). , 7-12 is more preferable), and an aryl group is preferable.

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

Rb ¹¹ and ^{Rb 12} have the same meanings as ^{Rb 11} and ^{Rb 12} in the formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.

The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.

The content of the other thermal base generator is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermal base generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Crosslinking agent>
The photosensitive resin composition of the present invention preferably contains a cross-linking agent.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.

<Radical cross-linking agent>
The photosensitive resin composition of the present invention preferably further contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.

The radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the ethylenically unsaturated bond.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the photosensitive resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable. The compound having is more preferable.
Further, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the photosensitive resin composition of the present invention has a compound having two ethylenically unsaturated bonds and three or more ethylenically unsaturated bonds. It is also preferable to contain a compound.

The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.

Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable. Esters of saturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0379193. Urethane (meth) acrylates as described above, polyester acrylates, epoxy resins and (meth) acrylics described in JP-A-48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as a preferable radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups and cardo resins can also be used.

Further, as other examples, the specific unsaturated compound described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the magazine of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.

Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, and their contents are incorporated in the present specification.

As radical cross-linking agents, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol residues or propylene glycol residues. A structure that is bonded via the above is preferable. These oligomer types can also be used.

Commercially available products of the radical cross-linking agent include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209 manufactured by Sartmer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, and urethane oligomer UAS-10. , UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.) And so on.

Examples of the radical cross-linking agent include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.

The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The radical cross-linking agent provided with the above is more preferable. Particularly preferably, in a radical cross-linking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good. On the other hand, from the viewpoint of the development speed in the case of alkaline development, the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.

In the photosensitive resin composition of the present invention, it is preferable to use a bifunctional metal acrylate or acrylate from the viewpoint of pattern resolution and film elasticity. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene. Glycoglycyl diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethyrol-tricyclodecanediacrylate, dimethyrol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adux glycol dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylate having a urethane bond can be used. can. If necessary, two or more of these can be mixed and used.
Further, from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured film), a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent. Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) N-vinyl compounds such as acrylic acid derivatives, N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate and triallyl trimellitate are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

When a radical cross-linking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

The radical cross-linking agent may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably in the above range.

<Other cross-linking agents>
It is also preferable that the photosensitive resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer. It is preferable that the compound has a plurality of groups in the molecule that promote the formation reaction, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of the acid or the base. A compound having a plurality of groups promoted by the above in the molecule is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator which is a photosensitizer in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom. A compound having a structure directly bonded to is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group. Examples thereof include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and melamine, which will be described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.

Specific examples of the melamine-based cross-linking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycol-uryl-based cross-linking agent;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.

Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples thereof include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which a group is directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like.

Commercially available products may be used as other cross-linking agents, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikarak (registered trademark, the same applies hereinafter) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ) And so on.

Further, it is also preferable that the photosensitive resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.

[Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the photosensitive resin composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propanetriglycidyl ether or the like alkylene glycol type epoxy resin or polyhydric alcohol hydrocarbon type epoxy resin; polypropylene glycol diglycidyl ether or the like polyalkylene glycol type epoxy resin; polymethyl (glycidyloxypropyl) siloxane or the like epoxy group Examples include, but are not limited to, the contained silicone. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron® EXA-4816, Epicron® EXA-4822, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron (Registered Trademark) EXA-8169, Epicron (Registered Trademark) N-660, Epicron (Registered Trademark) N-665-EXP-S, Epicron (Registered Trademark) N-740, Rica Resin (Registered Trademark) BEO-20E (the above products) Name, manufactured by DIC Co., Ltd., Rica Resin (registered trademark) BEO-60E, Rica Resin (registered trademark) HBE-100, Rica Resin (registered trademark) DME-100, Rica Resin (registered trademark) L-200 (trade name, New Japan) Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA Co., Ltd.), Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Epolyde GT400, Servinus B0134, B0177 (trade name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000 -L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201 , BREN-S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like.

[Oxetane compound (compound having an oxetanyl group)]
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.

[Benzoxazine compound (compound having a benzoxazolyl group)]
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly. Examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.

<Compounds having a sulfonamide structure, compounds having a thiourea structure>
From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the photosensitive resin composition of the present invention was selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to further contain at least one compound.

[Compound having a sulfonamide structure]
The sulfonamide structure is a structure represented by the following formula (S-1).

In the formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * may independently form a binding site with another structure. show.
The R is preferably the same group as ^{R 2} in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, ^{and two or more of R 1} , R ² and R ³ are bonded to each other. It may form a ring structure.
It is preferable that R ¹ , R ² and R ³ are independently monovalent organic groups.
Examples of R ¹ , R ² and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group and a carboxy group. Examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.

Among these, ^{compounds in which R 1} is an aryl group and R ² and R ³ are independently hydrogen atoms or alkyl groups are preferable.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1. -Sulfonamide, Naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N, N-dimethylmethanesulfonamide, N, N-dimethylethanesulfonamide, N, N-diethyl Examples thereof include methanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide and the like.

[Compound with thiourea structure]
The thiourea structure is a structure represented by the following formula (T-1).

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ⁴ and R ⁵ may be bonded to form a ring structure, where R ⁴ is. * it is may form a ring structure and other structures that bind, R ⁵ may form a ring structure and other structures that bind *, * is independently other Represents the site of connection with the structure of.

It is preferable that R ⁴ and R ⁵ are independently hydrogen atoms.
Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, and a carbonyl group. Examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.
The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferable.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).

In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and ^{at least two of R 4} to R ⁷ are bonded to each other to form a ring structure. You may.

Wherein (T-2), ^{R 4} and ^{R 5} have the same meanings as ^{R 4} and ^{R 5} in formula (T-1), a preferable embodiment thereof is also the same.
In the formula (T-2), ^{it is preferable that R 6} and R ⁷ are independently monovalent organic groups.
In the formula (T-2), the preferred embodiment of the monovalent organic group in ^{R 6} and R ⁷ is the same as the preferred embodiment of the monovalent organic group in ^{R 4} and R ^{5 in the formula (T-1).} ..

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoylthiourea, N, N'-. Diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethyl Examples thereof include thiourea, tetramethylthiourea, N, N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydrantin.

〔Content〕
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the photosensitive resin composition of the present invention. %, More preferably 0.2 to 3% by mass.
The photosensitive resin composition of the present invention may contain only one kind of compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more kinds. When only one kind is contained, the content of the compound is preferably in the above range, and when two or more kinds are contained, the total amount thereof is preferably in the above range.

<Polymerization inhibitor>
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4 -Methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N-sulfopropylamino) phenol, N- Nitrosophenyl hydroxyamine first cerium salt, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane, N, N'-diphenyl-p -Phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6- Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl-free radical, phenothiazine , 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. It is preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds can be used (Me is a methyl group).

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass.

The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>
The photosensitive resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfonamide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound and the like. And so on.

Examples of the silane coupling agent include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992. The compounds described in 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples include the compounds described in paragraph 0055. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glyceride. Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine , N-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanule, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Examples thereof include propyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.

Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..

The content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more kinds are used, the total amount is preferably in the above range.

<Other additives>
The photosensitive resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, to the extent that the effects of the present invention can be obtained. , Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, antiaggregating agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

[Sensitizer]
The photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with the thermal curing accelerator, the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzilidenindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Kumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naft (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4'-dimethylacetanilide and the like.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof is incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent]
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

[Surfactant]
A surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain indicate the number of repetitions of each repeating unit.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.

Examples of the hydrocarbon-based surfactant include Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin. D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (all manufactured by Takemoto Oil & Fat Co., Ltd.) and the like can be mentioned.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic® L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd. (Nissin Chemical Industry Co., Ltd.) Made by Co., Ltd.).

Specifically, as a cationic surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

Specific examples of the anion-type surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

[Higher fatty acid derivative]
In the photosensitive resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the photosensitive resin composition is dried in the process of application and drying. It may be unevenly distributed on the surface of an object.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

[Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing the inorganic particles having the average particle size, it is possible to achieve both the mechanical properties of the cured film and the suppression of scattering of the exposure light.

[UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Further, as an example of the triazine-based ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2) , 4-Dimethylphenyl) -1,3,5-Triazine and other bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) )-1,3,5-Triazine, 2,4,6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-Triazine, 2,4,6-Tris [2-Hydroxy-4 -(3-Butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-Triazine and other tris (hydroxyphenyl) triazine compounds and the like can be mentioned.

In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetoneate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.

When the organic titanium compound is blended, the blending amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the precursor of the cyclized resin. .. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.

〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).

In the general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R6 represents an alkylene group having 2 or more carbon atoms. R7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. k represents an integer of 1 to 4.

The compound represented by the general formula (3) suppresses oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust preventive action on the metal material.

Since it can act on the resin and the metal material at the same time, k is more preferably an integer of 2 to 4. Examples of R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-. Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. preferable.

Examples of the compound represented by the following general formula (3) include the following, but the compound is not limited to the following structure.

 

The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. When the addition amount is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation property after reliability and the adhesion to the metal material, and when the addition amount is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of reducing the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<Restrictions on other contained substances>
The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.6% by mass, from the viewpoint of coating surface properties. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.

From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, still more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.

Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as the raw material constituting the photosensitive resin composition of the present invention. Methods such as filtering the raw materials constituting the photosensitive resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible are mentioned. be able to.

Considering the use as a semiconductor material, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass by mass, from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

A conventionally known storage container can be used as the storage container for the photosensitive resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing contamination of raw materials and photosensitive resin compositions with impurities, a multi-layer bottle having an inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in JP-A-2015-123351.

<Use of photosensitive resin composition>
The photosensitive resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.

<Preparation of photosensitive resin composition>
The photosensitive resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the photosensitive resin composition. The filter hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is further preferable. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(Resin film, cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a resin film, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention or the resin film of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminated body of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are photosensitive of the present invention. A preferred embodiment is a film formed by curing the resin composition. The photosensitive resin composition of the present invention used for forming the first cured film and the photosensitive resin composition of the present invention used for forming the second cured film have the same composition. It may be present or it may be a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

Examples of the applicable field of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.

Further, the cured film in the present invention can also be used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as “the method for producing the present invention”) is a film forming in which the photosensitive resin composition of the present invention is applied to a substrate to form a film (resin film). It is preferable to include a step.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
Further, it is more preferable that the method for producing a cured film of the present invention includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying the photosensitive resin composition to a substrate to form a film (photosensitive resin composition layer) (b) After the film forming step, an exposure step of exposing the film (c) is exposed. Development step for developing the developed film (d) Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed, and sufficient curability is obtained.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. In the method for producing the laminated body of the present embodiment, after forming the cured film according to the above-mentioned method for producing the cured film, the steps (a), the steps (a) to (c), or (a) are further performed. )-(D). In particular, it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.

<Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the photosensitive resin composition is applied to a substrate to form a film (layered).

The type of substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like. Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
Further, as the base material, for example, a plate-shaped base material (board) is used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

Further, when the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.

Coating is preferable as a means for applying the photosensitive resin composition to the substrate.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, depending on the viscosity of the resin composition and the film thickness to be set, it is also preferable to apply the resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain uniformity of the film thickness, it is also possible to apply a combination of a plurality of rotation speeds.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
Further, a step of removing the excess film at the end portion of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like.
Further, a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.

<Drying process>
The production method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step). The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 3 minutes to 7 minutes.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (photosensitive resin composition layer). The exposure amount is not particularly determined as long as the photosensitive resin composition can be cured, but for example, ^{it is preferable to irradiate 100 to 10,000 mJ / cm 2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm ^2.

The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. The photosensitive resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i lines) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.

<Development process>
The production method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (photosensitive resin composition layer). By developing, the unexposed portion (non-exposed portion) is removed if it is a negative type. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a substrate, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves, and a combination thereof. Processes can be adopted.

Development is performed using a developer. As the developer, if it is a negative type, a developer from which an unexposed portion (non-exposed portion) is removed can be used without particular limitation.
As the developing solution, a developing solution containing an organic solvent or an alkaline aqueous solution can be used.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

When the developing solution is a developing solution containing an organic solvent, the organic solvent may be, for example, as esters such as ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate. , Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) , 3-Methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, 2-alkyloxypropionate) Methyl, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2) -Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol. Dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol mono As propyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example, toluene. , Xylene, anisole, limonene and the like, dimethyl sulfoxide is preferably mentioned as a sulfoxide, and a mixture of these organic solvents is also preferably mentioned.

When the developer is a developer containing an organic solvent, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention. When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more.

When the developer is a developer containing an organic solvent, 50% by mass or more of the developer is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is organic. It is more preferably a solvent. Further, the developer may be 100% by mass of an organic solvent.

The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.

When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. .. When TMAH is used, for example, the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.

[Method of supplying developer]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and a method of immersing the base material in the developer, a method of supplying the developer on the base material using a nozzle and paddle development, or continuous development. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
The method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.

The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly determined, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.

After the treatment with the developer, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the photosensitive resin composition.
When the developer is a developer containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA. Further, water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.

When the rinsing solution contains an organic solvent, the ethers include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid). Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2) -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion) Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate). Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran. , Ethyl Glycol Monomethyl Ether, Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons. For example, toluene, xylene, anisole, limonene and the like, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols. Glycols and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.

When the rinsing liquid contains an organic solvent, one type or a mixture of two or more types of organic solvent can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferable, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.

When the rinsing liquid contains an organic solvent, 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable. Further, the rinse liquid may be 100% by mass of an organic solvent.

The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoaming agents.

[Supplying method of rinse liquid]
The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid on the base material by filling, and the method of supplying the rinsing liquid to the base material with a shower. There are a method of supplying the rinse liquid and a method of continuously supplying the rinse liquid onto the base material by means such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the film after exposure by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sonic or the like and a process of combining them can be adopted.

<Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, the photosensitive resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but may also cure a radically polymerizable compound other than the precursor which is an unreacted specific resin. It can be advanced in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured membrane can be prevented from excessive volatilization. Residual stress can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out the heating from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.

The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and even more preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

Particularly when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and the temperature is kept at 200 ° C. for 120 minutes. , Such as a pretreatment step may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.

Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.

<Metal layer forming process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (photosensitive resin composition layer).

As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified. The alloy containing the above is more preferable, and copper is further preferable.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, still more preferably 1 to 10 μm in the thickest portion.

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

In the laminating step, (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, it may be an embodiment in which only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated photosensitive resin composition layers all at once. Further, the (c) developing step may include (e) a metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step and the like as appropriate.

When the laminating step is further performed, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment.

The laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.
Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.

For example, a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the photosensitive resin composition so as to cover the metal layer after the metal layer is provided. Specifically, an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle. By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin layer) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

(Surface activation treatment process)
The method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the exposure development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step and then the metal layer forming step. good.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer that forms the photosensitive resin composition layer on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. As described above, by performing the surface activating treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment.
Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF ₄ / O _2. Etching treatment with NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment with ultraviolet (UV) ozone method, soaking in a hydrochloric acid aqueous solution to remove the oxide film, and then removing amino and thiol groups. It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500 ~ 200,000J / ^{m 2,} more preferably 1000 ~ 100,000J / ^{m 2,} and most preferably 10,000 ~ 50,000J / ^{m 2.}

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the photosensitive resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis Example B-1: Synthesis of Compound B-1>
In a flask equipped with a stirrer and a condenser, 8.75 g (52.5 mmol) of cinnamoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50 g of ethyl acetate and cooled to 0 ° C. Next, 4.35 g (55 mmol) of pyridine and 8.97 g (50 mmol) of triethoxy-3-aminopropylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 20 g of ethyl acetate, and then a dropping funnel was used for 1 hour. Dropped over. After stirring at 0 ° C. for 1 hour, the mixture was stirred at 25 ° C. for 2 hours. Then, it was dissolved in 600 mL of ethyl acetate and transferred to a separating funnel. This was then washed once with 100 mL of water, twice with 100 mL of saturated aqueous sodium hydrogen carbonate, twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 12 g of compound B-1. The fact that it was compound B-1 was ^{confirmed from 1 1} H-NMR spectrum.
The structure of compound B-1 is presumed to be the structure represented by the following formula (B-1).

<Synthesis Examples B-2 to B-5: Synthesis of Compounds B-2 to B-5, B-7, B-8>
Compounds B-2 to B-5, B-7, and B-8 were synthesized by the same method as in Synthesis Example B-1.
The presumed structures of the compounds B-2 to B-5 are shown in the following formulas (B-2) to (B-5), formulas (B-7), and (B-8), respectively.

<Synthesis Example B-6: Synthesis of Compound B-6>
In a flask equipped with a stirrer and a condenser, 8.57 g (52.5 mmol) of 4-aminocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 g of tetrahydrofuran and stirred at 25 ° C. Then, 12.4 g (50 mmol) of 3- (triethoxysilyl) propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 20 g of tetrahydrofuran, and then added dropwise over 1 hour with a dropping funnel. Then, the mixture was stirred at 25 ° C. for 3 hours. Then, it was dissolved in 800 mL of ethyl acetate and transferred to a separating funnel. This was then washed once with 100 mL of water, twice with 100 mL of saturated aqueous sodium hydrogen carbonate, twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 16 g of compound B-6. The fact that it was compound B-6 was ^{confirmed from 1 1} H-NMR spectrum.
The structure of compound B-6 is presumed to be the structure represented by the following formula (B-6).

<Synthesis Examples B-9 and B-10: Synthesis of Compounds B-9 and B-10>
In a flask equipped with a stirrer and a condenser, 8.06 g (50 mmol) of 7-amino-4 methylcoumarin (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 g of tetrahydrofuran. Then, 12.4 g (50 mmol) of 3- (triethoxysilyl) propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise using a dropping funnel over 1 hour, and the mixture was stirred at 25 ° C. for 2 hours. Then, it was dissolved in 600 mL of ethyl acetate and transferred to a separating funnel. This was then washed once with 100 mL of water, twice with 100 mL of saturated aqueous sodium hydrogen carbonate, twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 16 g of compound B-9. The fact that it was compound B-9 was ^{confirmed from 1 1} H-NMR spectrum.
The structure of compound B-9 is presumed to be the structure represented by the following formula (B-9).
Compound B-10 was synthesized by the same method as in Synthesis Example B-9. The structure of compound B-10 is presumed to be the structure represented by the following formula (B-10).

<Synthesis Example M-1: Synthesis of Compound M-1>
In a flask equipped with a stirrer and a condenser, 8.75 g (52.5 mmol) of cinnamoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50 g of ethyl acetate and cooled to 0 ° C. Next, 4.35 g (55 mmol) of pyridine and 6.57 g (50 mmol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 20 g of ethyl acetate, and then a dropping funnel was used for 1 hour. Dropped. After stirring at 0 ° C. for 1 hour, the mixture was stirred at 25 ° C. for 2 hours. Then, it was dissolved in 600 mL of ethyl acetate and transferred to a separating funnel. This was then washed once with 100 mL of water, twice with 100 mL of saturated aqueous sodium hydrogen carbonate, twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 12 g of compound M-1. The fact that it was compound M-1 was ^{confirmed from 1 1} H-NMR spectrum.
The structure of compound M-1 is presumed to be the structure represented by the following formula (M-1).

<Synthesis Example PB-1: Synthesis of Compound PB-1>
15 g of propylene glycol monomethyl ether was added to the flask, the temperature was raised to 80 ° C. while flowing nitrogen, and the mixture was stirred.
Next, in an Erlenmeyer flask, 14.52 g (50 mmol) of 3- (triethoxysilyl) propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 13.15 g (50 mmol) of M-1, and propylene glycol monomethyl ether were placed. 50 g and 0.46 g of the polymerization initiator V-601 (manufactured by Fujifilm Wako Co., Ltd.) were added, dissolved, and added dropwise to the flask over 3 hours. Then, the temperature was raised to 85 ° C., the mixture was stirred for 3 hours, and then cooled to room temperature to obtain a PB-1 solution. The solid content concentration (solid content amount / total mass of the solution × 100) of the obtained PB-1 solution was 30% by mass, and the weight average molecular weight (Mw) of PB-1 was 20,500.
The structure of PB-1 is presumed to be the structure represented by the following formula (PB-1). In the following formula, the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit.

<Synthesis Example M-2: Synthesis of Compound M-2>
In a flask equipped with a stirrer and a condenser, 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.25 g (105 mmol), Karenz MOI (manufactured by Showa Denko Co., Ltd.) 15.52 g (100) Mt. mmol) and 0.01 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) were dissolved in 70 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 25 ° C. for 1 hour. Then, after stirring at 45 ° C. for 2 hours, the mixture was dissolved in 600 mL of ethyl acetate and transferred to a separating funnel. It was then washed twice with 100 mL of water and twice with 150 mL of saturated brine and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 18 g of compound M-2. The fact that it was compound M-2 was ^{confirmed from 1 1} H-NMR spectrum.
The structure of compound M-2 is presumed to be the structure represented by the following formula (M-2).

<Synthesis example PC-1: Synthesis of compound PC-1>
15 g of propylene glycol monomethyl ether was added to the flask, the temperature was raised to 80 ° C. while flowing nitrogen, and the mixture was stirred.
Next, in the flask, 11.21 g (50 mmol) of M-2 (the synthetic product), 13.15 g (50 mmol) of M-1, 50 g of propylene glycol monomethyl ether, and the polymerization initiator V-601 (Fujifilm). 0.46 g (manufactured by Wako Co., Ltd.) was added, dissolved, and added dropwise to the flask over 3 hours. Then, the temperature was raised to 85 ° C., the mixture was stirred for 3 hours, and then cooled to room temperature to obtain a PC-1 solution.
The structure of PC-1 is presumed to be the structure represented by the following formula (PC-1). In the following formula, the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit. The Mw of PC-1 was 15,000.

<Synthesis Example CA-1: Synthesis of Compound CA-1>
In a flask equipped with a stirrer and a condenser, 3.39 g (55 mmol) of 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.35 g (55 mmol) of pyridine were dissolved in 50 g of tetrahydrofuran. It was cooled to 0 ° C. Next, 8.33 g (50 mmol) of cinnamoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 30 g of tetrahydrofuran, and then added dropwise with a dropping funnel over 1 hour. After stirring at 0 ° C. for 1 hour, the mixture was stirred at 25 ° C. for 2 hours. Then, it was dissolved in 400 mL of ethyl acetate and transferred to a separating funnel. This was then washed once with 100 mL of water, twice with 100 mL of saturated aqueous sodium hydrogen carbonate, twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 10 g of compound CA-1. The fact that it was compound CA-1 was ^{confirmed from 1 1} H-NMR spectrum.
The structure of compound CA-1 is presumed to be the structure represented by the following formula (CA-1).

<Synthesis Examples CA-2 and CA-3: Synthesis of Compounds CA-2 and CA-3>
Compounds CA-2 and CA-3 were synthesized by the same method as in Synthesis Example CA-1.
The structures of the compounds CA-2 and CA-3 are presumed to be the structures represented by the following formula (CA-2) or the following formula (CA-3), respectively.

<Synthesis Example A-1: Synthesis of polybenzoxazole precursor A-1 from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride>
28.0 g (76.4 mmol) of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone by stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was added to 75 g of N-methylpyrrolidone while keeping the temperature at -10 to 0 ° C. The dissolved solution was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was filtered off, stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polybenzoxazole precursor A-1. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of this polybenzoxazole precursor A-1 were Mw = 21500 and Mn = 9500.
The structure of the polybenzoxazole precursor A-1 is presumed to be the structure represented by the following formula (A-1).

<Synthesis Example A-2: Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate>
14.06 g (64.5 mmol) of pyromellitic acid dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. 20.4 g (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was _{chlorinated with SOCL 2} and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and in the same manner as in Synthesis Example A-5. Polyimide precursor A-2 was obtained. The weight average molecular weight of this polyimide precursor A-2 was 21,000.
The structure of the polyimide precursor A-2 is presumed to be the structure represented by the following formula (A-2).

<Synthesis Example A-3: Polyimide precursor from 4,4'-oxydiphthalic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: Polyimide precursor having a radically polymerizable group) ) Synthesis>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g. Hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to give a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethylmethacrylate. Manufactured. Next, the obtained diester was _{chlorinated with SOCL 2} and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and in the same manner as in Synthesis Example A-5. Polyimide precursor A-3 was obtained. The weight average molecular weight of this polyimide precursor A-3 was 19,600.
The structure of the polyimide precursor A-3 is presumed to be the structure represented by the following formula (A-3).

<Synthesis Example A-4: Polyimide precursor from 4,4'-oxydiphthalic acid dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) and 2-hydroxyethylmethacrylate (A-4) : Synthesis of polyimide precursor with radically polymerizable group)>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g. Hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to give a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethylmethacrylate. Manufactured. Next, the obtained diester was _{chlorinated with SOCL 2} , and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example A-5, and synthesized Example A. Polyimide precursor A-4 was obtained in the same manner as in −5. The weight average molecular weight of this polyimide precursor A-4 was 23,500.
The structure of the polyimide precursor A-4 is presumed to be the structure represented by the following formula (A-4).

<Synthesis Example A-5: Synthesis of polyimide precursor resin A-5 from oxydiphthalic acid dianhydride, 4,4'-biphthalic acid anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether>
9.49 g (32.25 mmol) of 4,4'-biphthalic acid anhydride, oxydiphthalic acid dianhydride while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. 10.0 g (32.25 mmol) of the product was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours before adding 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent solution by dropping over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor A-5. The obtained polyimide precursor A-5 had a weight average molecular weight of 23,800 and a number average molecular weight of 10,400.
The structure of the polyimide precursor A-5 is presumed to be the structure represented by the following formula (A-5).

<Synthesis Example A-6: Synthesis of Polyimide Precursor A-6 from 4,4'-oxydiphthaldiate anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>
155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 mL of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and the mixture was stirred for 1 hour. Then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polyimide precursor A-6. The weight average molecular weight (Mw) of this polyimide precursor A-6 was measured and found to be 24,000.

<Synthesis Example A-7: Synthesis of polyimide precursor A-7 from 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>
Synthesis Example 6 except that 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride. Polymer A-7 was obtained by carrying out the reaction in the same manner as described in 6. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,900.

<Synthesis Example PBI-1: Synthesis of Polyimide PBI-1>
In a flask equipped with a condenser and a stirrer, while removing water, 4,4'-(hexafluoroisopropyridene) diphthalic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.2 g (50 mmol), 2 , 2,6,6-Tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.02 g was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Then, 11.9 g (45 mmol) of diamine (AA-1) described later was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours, and 50 g of N-methylpyrrolidone (NMP) was added. Was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3000 rpm for 15 minutes. The resin was filtered off, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw = 19,000 and Mn = 8,100.
It is presumed that the structure of polyimide PBI-1 is a structure represented by the following formula (PBI-1).

<Synthesis Example AA-1: Synthesis of Diamine AA-1>
2-Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 26.0 g (0.2 mol), dehydrated pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) in a flask equipped with a condenser and a stirrer. ) 17.4 g (0.22 mol) was dissolved in 78 g of ethyl acetate and cooled to 5 ° C. or lower. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was dissolved in a flask over 1 hour using a dropping funnel. Dropped into. After completion of the dropping, the mixture was stirred at 10 ° C. or lower for 30 minutes, heated to 25 ° C., and stirred for 3 hours. Then, the reaction solution was _{diluted with 600 mL of ethyl acetate (CH 3} COOEt), transferred to a separating funnel, and washed with 300 mL of water, 300 mL of saturated aqueous sodium hydrogen carbonate, 300 mL of dilute hydrochloric acid, and 300 mL of saturated brine in that order. After liquid separation washing, drying with 30 g of magnesium sulfate, concentration using an evaporator, and vacuum drying were performed to obtain 61.0 g of a dinitro compound (A-1).
27.9 g (500 mmol) of reduced iron (manufactured by Wako Pure Chemical Industries, Ltd.) and 5.9 g (110 mmol) of ammonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in a flask equipped with a condenser and a stirrer. ), Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 3.0 g (50 mmol), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.03 g Was weighed, 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added, and the mixture was stirred.
Then, 16.2 g of the dinitro compound (A-1) was added little by little over 1 hour, and the mixture was stirred for 30 minutes. Next, the outside temperature was raised to 85 ° C., the mixture was stirred for 2 hours, cooled to 25 ° C. or lower, and then filtered using Cerite (registered trademark). The filtrate was concentrated on a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separating funnel, washed twice with 300 mL of saturated aqueous sodium hydrogen carbonate, and then washed with 300 mL of water and 300 mL of saturated brine in that order. After liquid separation washing, drying with 30 g of magnesium sulfate, concentration using an evaporator, and vacuum drying were performed to obtain 11.0 g of diamine (AA-1).

<Examples and comparative examples>
In each example, the components listed in the table below were mixed to obtain each photosensitive resin composition. Further, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition.
Specifically, the content of the components other than the solvent described in the table is the amount (parts by mass) described in each "addition amount" column of the table.
PB-1 and PC-1 were added so that the amount of solid content in the solution was the amount (part by mass) described in each "addition amount" in the table.
The obtained photosensitive resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.

The details of each component listed in the table are as follows.

〔resin〕
A-1 to A-7, PBI-1: Polybenzoxazole precursor A-1, polyimide precursors A-2 to A-7, polyimide PBI-1 synthesized in the above synthesis example.

[A group capable of photodimerization reaction and a compound having an alkoxysilyl group]
B-1 to B-10: B-1 to B-10 synthesized in the above synthesis example.
PB-1: PB-1 synthesized in the above synthesis example
PB-1 is a resin having a group capable of photodimerization reaction and an alkoxysilyl group.

[Compound having an azole group (a compound having neither a photodiquantifying reaction group nor an alkoxysilyl group and having an azole group)]
C-1 to C-7: Compounds represented by the following formulas (C-1) to (C-7)

[Azole group and a compound having a photodimerization reactionable group (a compound having no alkoxysilyl group and having a photodimerification reaction, and a compound having an azole group)]
-CA-1 to CA-3: Compounds represented by the following formulas (CA-1) to (CA-3)-PC-1: PC-1 synthesized in the above synthesis example
PC-1 is a resin having an azole group and a group capable of photodimerization reaction.

[Metal adhesion improver]
D-1 to D-3: Compounds represented by the following formulas (D-1) to (D-3)

[Photopolymerization initiator (both are trade names)]
・ OXE-01: IRGACURE OXE 01 (manufactured by BASF)
OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compounds (both trade names)]
-SR-209: SR-209 (manufactured by Sartmer)
-SR-231: SR-231 (manufactured by Sartmer)
-SR-239: SR-239 (manufactured by Sartmer)
-A-DPH: Dipentaerythritol hexaacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

[Polymerization inhibitor]
G-1: 1,4-benzoquinone, G-2: 4-methoxyphenol, G-3: 1,4-dihydroxybenzene, G-4: a compound having the following structure

[Base generator]
-H-1 to H-3: Compounds with the following structure-H-4: WPBG-27 (Fuji Film Wako Pure Chemical Industries, Ltd.)

[Other additives]
・ I-1: N-Phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

〔solvent〕
-DMSO: dimethyl sulfoxide-GBL: γ-butyrolactone-NMP: N-methylpyrrolidone In the table, "DMSO / GBL" is a mixture of DMSO and GBL at a mixing ratio (mass ratio) of 80:20. It is shown that.

<Evaluation>
[Evaluation of copper adhesion]
Each of the photosensitive resin compositions or comparative compositions after filtration was applied in layers on a copper substrate by a spin coating method to form a photosensitive resin composition layer. The copper substrate to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 μm on the copper substrate. The photosensitive resin composition layer on the copper substrate was subjected to a stepper (Nikon NSR 2005 i9C) using a photomask in which a 100 μm square non-masked portion was formed with an exposure energy of ^{500 mJ / cm 2.} It was exposed and then developed with cyclopentanone for 60 seconds to obtain a 100 μm square resin layer. Further, the temperature is raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching the temperature described in the column of "curing temperature (° C.)" in the table, this temperature is maintained for 3 hours to form a resin film. I got 2.
However, in the example in which I-4 was used as the base generator, after reaching the temperature described in the above "curing temperature (° C.)" column, the pattern was subjected to an exposure amount of ^{500 mJ / cm 2 while being maintained for 3 hours.} The i-exposure was performed on the entire surface.
Shear force was measured on a 100 μm square resin film 2 on a copper substrate in an environment of 25 ° C. and 65% relative humidity (RH) using a bond tester (CondorSigma, manufactured by XYZTEC). It can be said that the larger the shearing force, the larger the adhesion force and the excellent adhesion between the metal and the cured film, which is a preferable result.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Copper adhesion" column in the table.
-Evaluation criteria-
A: Shear force exceeds 40 gf B: Shear force exceeds 35 gf and 40 gf or less C: Shear force exceeds 30 gf and 35 gf or less D: Shear force exceeds 25 gf and 30 gf or less E: Shear force exceeds 25 gf 1 gf Is 9.80665 × 10 ^-3 N.

[Evaluation of pattern formation]
Each photosensitive resin composition or comparative composition was applied onto a silicon wafer by a spin coating method (3,500 rpm, 30 seconds). The silicon wafer to which the composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform polymer layer having a thickness of 10 μm on the silicon wafer.
-exposure-
The polymer layer on the silicon wafer was exposed with an aligner (Kall-Suss MA150). The exposure was performed with a high-pressure mercury lamp, and the exposure amount was set to the exposure amount that minimizes the line width described later. The exposure was performed through a photomask in which a 1: 1 line-and-space pattern in 1 μm increments was formed from a line width of 5 μm to 25 μm. The exposure energy with a wavelength of 365 nm required to make a good structure was confirmed.
-Pattern formation-
After exposure, it was developed with cyclopentanone for 60 seconds to form a pattern. The line width that could have good edge sharpness was evaluated according to the following evaluation criteria. The smaller the line width, the larger the difference in solubility between the light-irradiated part and the non-light-irradiated part in the developing solution, and the smaller the difference in the solubility of the exposed part between the upper layer part and the lower layer part of the film in the developing solution. This is a preferable result because the pattern forming property is good.
-Evaluation criteria-
A: More than 5 μm and 10 μm or less B: More than 10 μm and 15 μm or less C: More than 15 μm and 20 μm or less D: More than 20 μm.

From the above results, it can be seen that the photosensitive resin composition according to the present invention is excellent in pattern forming property.
The comparative compositions according to Comparative Examples 1 to 3 do not contain a compound capable of a photodimerization reaction and a compound having an alkoxysilyl group.
It can be seen that such a comparative composition is inferior in pattern forming property.

<Example 101>
The photosensitive resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a photosensitive resin composition layer having a thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims (15)

1. At least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides and polybenzoxazoles, and
   A photosensitive resin composition containing a group capable of a photodimerization reaction and compound B, which is a compound having an alkoxysilyl group.
2. The photosensitive resin composition according to claim 1, wherein the photodimerizable group in the compound B has a cinnamoyl structure, a coumarin structure, a naphthalene structure, or an anthracene structure.
3. The photosensitive resin composition according to claim 1 or 2, wherein the compound B is a compound represented by the following formula (1-1) or the following formula (1-2).
   

   

   In formula (1-1), R ¹ independently represents a monovalent organic group, n represents an integer of 0 to 5, and T ¹ and T ² independently represent a hydrogen atom or a monovalent organic. A group is represented, X ¹ is a divalent linking group, and Z ¹ is an alkoxysilyl group.
   In formula (1-2), R ¹ independently represents a monovalent organic group, m represents an integer of 0 to 4, and T ³ to T ⁶ independently represent a hydrogen atom or a monovalent organic. Representing a group, X ² and X ³ each independently represent a divalent linking group, and Z ² and Z ³ each independently represent an alkoxysilyl group.
4. The photosensitive according to any one of claims 1 to 3, further comprising compound C, which is a compound having no at least one of a photodimerizable group and an alkoxysilyl group and having an azole group. Resin composition.
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound C is a compound having no alkoxysilyl group, a group capable of photodimerization reaction, and an azole group.
6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the compound C is a resin.
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the compound B is a resin.
8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the compound B contains an azole group.
9. The photosensitive resin composition according to any one of claims 1 to 8, which is used for forming an interlayer insulating film for a rewiring layer.
10. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 9.
11. A laminate containing two or more layers of the cured film according to claim 10 and containing a metal layer between any of the cured films.
12. A method for producing a cured film, which comprises a film forming step of applying the photosensitive resin composition according to any one of claims 1 to 9 to a substrate to form a film.
13. The method for producing a cured film according to claim 12, further comprising an exposure step for exposing the film and a developing step for developing the film.
14. The method for producing a cured film according to claim 12, which comprises a heating step of heating the film at 50 to 450 ° C.
15. A semiconductor device comprising the cured film according to claim 10 or the laminate according to claim 11.